CN1684658A - Use of polymers based on N-vinyl caprolactam - Google Patents

Use of polymers based on N-vinyl caprolactam Download PDF

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CN1684658A
CN1684658A CN03823185.9A CN03823185A CN1684658A CN 1684658 A CN1684658 A CN 1684658A CN 03823185 A CN03823185 A CN 03823185A CN 1684658 A CN1684658 A CN 1684658A
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polymer
acid
ester
weight
vinyl
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CN100515383C (en
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G·米勒
P·赫斯塞尔
T·施奈德
C·伍德
K·马特豪尔
C·德罗曼
S·源-金
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BASF SE
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/04—Preparations for permanent waving or straightening the hair

Abstract

The invention relates to cosmetic preparations, particularly for hair cosmetic applications, containing copolymers based on N-vinyl lactams and N-vinyl heterocyclic compounds.

Description

Purposes based on the polymer of N-caprolactam
The present invention relates to cosmetic formulations, especially for the cosmetic formulations that hair cosmetic is used, it comprises the copolymer based on N-vinyl lactam and N-vinyl heterocyclic compound.
Prior art
The copolymer that comprises the N-vinyl lactam is used for cosmetic formulations as Luviskol K, Luviskol VA, LuviquatHold or Luviskol Plus (BASF), in the hair cosmetic preparation, especially as hair setting composition.
For hair cosmetic, the use of gel preparation is more and more.Hair setting composition and described gel preparation in this gellike preparation should satisfy following technical conditions, and promptly nontoxic, transparent, colourless, not sticking, good styling, hygroscopicity are not too big, have good denseness.
Here the copolymer of Shi Yonging also shows the improved performance of some needs.Remove some non-ionic copolymer, outside Luviskol K90, K30, Luviskol VA 64 (BASF) or polyvinyl formamide, most of gel all is muddy to opaque.The easy degree of suction and the viscosity of the hair of handling with these copolymers are higher equally.The typing effect equally also needs to improve.
Polymer of the present invention does not have above-mentioned shortcoming.Have now found that, cationicallyization, preferred content is no more than 5 weight %, and preferred 2-4 weight % contains the N monomer and especially can make the clear gel agent with good typing effect.Surprisingly, have now found that small amounts of monomer C can cause performance significantly to be improved.
DE-C 12 61 822 has described N-caprolactam and for example N-vinyl imidazole and N-vinylpyrrolidone copolymers.This copolymer is as with the pigment dyestuff dye liquor fibrous material being carried out reducing in the painted process reagent that migration takes place pigment.
EP 0 455 081 has described the copolymer of following component:
The N-caprolactam of 35-65 weight %,
The mixture of the 5-50 weight portion N-vinyl imidazole of 35-65 weight % and 10-60 weight portion N-vinyl pyrrolidone (it is equivalent to VI: VP (VI/VP) than between 1: 12 (1/12)-5: 1 (5/1)),
The monomer of the other free redical copolymerization of 0-4 weight %,
And this analog copolymer is as the purposes of hairspray and hair-care agent.
WO 9831328 has described aqueous compositions, and it comprises: (a) 0.1-10 weight %'s based on N-caprolactam, N-vinyl imidazole, N-vinylpyrrolidone copolymers and (b) at least a polyoxyethylene C of 0.1-10 weight % 6-C 15Monoalky lether, and their purposes in cosmetic formulations.
EP 0709411 has described soluble copolymers, and it contains at least a N-of being selected from caprolactam, the N-vinyl imidazole of 15-84.99 weight %, the monomer of N-vinyl pyrrolidone in alcoholic solution.
We have found that the purposes of polymer in hair cosmetic of following component:
1-98.9 the caprolactam of weight % (monomer A),
1-98.9 the vinyl pyrrolidone of weight % (monomers B),
0.1-5 the vinyl imidazole of weight % (monomer C),
The monomer D of 0-10 weight %,
The polymer E of 0-10 weight % (based on monomeric total amount),
Wherein the weight ratio of monomer C and monomers B (monomer C/ monomers B) is lower than 1: 12 (1/12).
The polymer of preferred following component:
The caprolactam (monomer A) of 30-59 weight %,
The vinyl pyrrolidone (monomers B) of 40-69 weight %,
The vinyl imidazole of 1-4 weight % (monomer C),
The monomer D of 0-10 weight %,
The polymer E of 0-10 weight % (based on monomeric total amount),
Wherein the weight ratio of monomer C and monomers B (monomer C/ monomers B) is lower than 1: 13.
Particularly preferably in hair cosmetic, especially use the polymer of following component in the hair setting composition:
The caprolactam (monomer A) of 35-50 weight %,
The vinyl pyrrolidone (monomers B) of 40-62 weight %,
The vinyl imidazole of 1-3 weight % (monomer C),
The monomer D of 0-10 weight %,
The polymer E of 0-10 weight % (based on monomeric total amount),
Wherein the weight ratio of monomer C and monomers B is less than or equal to 1: 14.
The ratio of preferred especially wherein monomer C and monomers B is less than or equal to 1: 15, and particularly 1: 20,1: 23 polymer especially.
N-caprolactam (monomer A) is interpreted as referring to N-vinyl-epsilon-caprolactams.The consumption of monomer A is 1-98.9 weight %, preferred 30-59 weight %, particularly 35-50 weight %.
Vinyl pyrrolidone is as monomers B.
The consumption of monomers B is 1-98.9 weight %, preferred 40-69 weight %, particularly 49-62 weight %.
As monomer C, use the vinyl imidazole of general formula X I, wherein R 40-R 42Be hydrogen independently of one another, C 1-C 4Alkyl or phenyl.Preferably, R 40-R 42Be hydrogen and methyl.
The consumption of monomer C is 0.1-5 weight %, preferred 1-4 weight %, particularly 1-3 weight %.
Following monomer can be used as monomer D:
The preferred ethylenic unsaturated material that uses in addition can be represented by following general formula:
X-C(O)CR 20＝CHR 19
Wherein:
X is selected from group-OH ,-OM ,-OR 21, NH 2,-NHR 21, N (R 21) 2
M is selected from following cation: Na +, K +, Mg ++, Ca ++, Zn ++, NH 4 +, alkyl phosphate ion, dialkyl ammonium ion, trialkyl ammonium ion and tetraalkyl ammonium ion;
Radicals R 21Can be identical or different and be selected from-H C 1-C 40Linearity or branched chain alkyl, N, N-dimethyl aminoethyl, 2-ethoxy, 2-methoxy ethyl, 2-ethoxyethyl group, hydroxypropyl, methoxy-propyl or ethoxycarbonyl propyl.
R 20And R 19Be independently from each other :-H, C 1-C 8Linearity or branched chain alkyl chain, methoxyl group, ethyoxyl, 2-hydroxy ethoxy, 2-methoxy ethoxy and 2-ethoxyethyl group.
Suitable monomers (D) but representative non-limiting instance be for example acrylic or methacrylic acid and salt, ester and amide.Described salt can be derived by the ammonium counter ion of any no noxious metals, ammonium or replacement and be obtained.
Described ester can be by C 1-C 40Linear chain, C 3-C 40Branched chain or C 3-C 40Carbocyclic alcohol, by the polyhydric alcohol with about 8 hydroxyls of 2-such as ethylene glycol, hexanediol, glycerol and 1,2, the 6-hexanetriol, by amino alcohol or by the aliphatic alcohol of alcohol ether such as methyl cellosolve and ethoxy ethanol, (alkyl) Polyethylene Glycol, (alkyl) polypropylene glycol or ethoxylation as with the C of 1-200 ethylene oxide unit reaction 12-C 24Aliphatic alcohol is derived and is obtained.
The suitable N that also has following general formula (VII), the acrylamide and the Methacrylamide of the acrylate of N-dialkyl aminoalkyl and methacrylate and N-dialkyl aminoalkyl:
Wherein:
R 22=H contains the alkyl of 1-8 carbon atom,
R 23=H, methyl,
R 24=containing the alkylidene of 1-24 carbon atom, it is chosen wantonly and is replaced by alkyl,
R 25, R 26=C 1-C 40Alkyl,
When g=1, Z=nitrogen, perhaps when g=0, Z=oxygen.
Described amide can be unsubstituted, N-alkyl or the mono-substituted or N of N-alkyl amino, the N-dialkyl group replaces or N, and the N-dialkyl amido is dibasic, and wherein alkyl or alkyl amino are derived from C 1-C 40Linear chain, C 3-C 40Branched chain or C 3-C 40The carbocyclic ring unit.In addition, alkyl amino can be quaternized.
The comonomer of preferred formula VII is (methyl) acrylic acid N, N-dimethylaminomethyl ester, (methyl) acrylic acid N, N diethylamino methyl ester, (methyl) acrylic acid N, N-dimethyl aminoethyl ester, (methyl) acrylic acid N, N-diethylamino ethyl ester, N-[3-(dimethylamino) propyl group] Methacrylamide and N-[3-(dimethylamino) propyl group] acrylamide.
Same operable monomer (D) is acrylic acid and salt, ester and the amide that replaces, and wherein the substituent group on the carbon atom and is independently from each other C on acrylic acid two or three-digit 1-C 4Alkyl ,-CN, COOH, special preferable methyl acrylic acid, ethylacrylic acid and 3-alpha-cyanoacrylate.Acrylic acid these salt, ester and the amide of these replacements can be selected for acrylic acid salt, ester and amide are described as above.
Other suitable monomers (D) is C 1-C 40Linear chain, C 3-C 40Branched chain or C 3-C 40The allyl ester of carbocyclic ring carboxylic acid; Vinyl or allyl halide, preferred vinyl chloride and allyl chloride; Vinyl ethers, preferable methyl, ethyl, butyl or dodecyl vinyl; Vinyl-or the heterocyclic compound of pi-allyl-replacement, optimal ethylene yl pyridines, second alkene oxazolin and allyl pyridine.
The suitable N-vinyl imidazole derivant that also has general formula VIII, wherein R 27-R 29Be hydrogen independently of one another, C 1-C 4Alkyl or phenyl:
Figure A0382318500071
Suitable monomers (D) is the diallylamine of general formula (IX) in addition:
R wherein 30=C 1-C 24Alkyl
Suitable monomers (D) is a vinylidene chloride in addition; With the hydrocarbon that contains at least one carbon-to-carbon double bond, optimization styrene, α-Jia Jibenyixi, t-butyl styrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butylene, 2-butylene, isobutene., vinyltoluene and these monomeric mixture.
Specially suitable comonomer (D) is an acrylic acid, methacrylic acid, ethylacrylic acid, acrylic acid methyl ester., ethyl acrylate, propyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, tert-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, metering system tert-butyl acrylate, methacrylic acid 2-ethyl hexyl ester, decyl-octyl methacrylate, the ethylacrylic acid methyl ester, ethyl propylene acetoacetic ester, the positive butyl ester of ethylacrylic acid, the ethylacrylic acid isobutyl ester, the ethyl propylene tert-butyl acrylate, ethylacrylic acid 2-ethyl hexyl ester, ethylacrylic acid ester in the last of the ten Heavenly stems, (methyl) stearyl acrylate base ester, acrylic acid 2,3-dihydroxypropyl ester, methacrylic acid 2,3-dihydroxypropyl ester, acrylic acid 2-hydroxyethyl ester, acrylic acid hydroxypropyl ester, methacrylic acid 2-hydroxyl ethyl ester, ethylacrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-methoxy ethyl ester, methacrylic acid 2-methoxy ethyl ester, ethylacrylic acid 2-methoxy ethyl ester, methacrylic acid 2-ethoxyethyl group ester, ethylacrylic acid 2-ethoxyethyl group ester, hydroxypropyl methacrylate, single acrylic acid glyceryl ester, monomethyl acrylic acid glyceryl ester, (methyl) acrylic acid poly alkylene glycol ester, unsaturated sulfonic acid is as the acrylamido propane sulfonic acid;
Acrylamide, Methacrylamide, ethyl acrylamide, N methacrylamide, N, the N-DMAA, the N-ethyl acrylamide, the N-N-isopropylacrylamide, N-butyl acrylamide, N tert butyl acrylamide, N-octyl acrylamide, uncle's N-octyl acrylamide, N-octadecyl acrylamide, N phenyl acrylamide, N-methyl acrylamide, N-ethyl-methyl acrylamide, N-dodecyl methyl acrylamide, the 1-vinyl imidazole, 1-vinyl-2-methyl ethylene imidazoles, (methyl) acrylic acid N, N-dimethylaminomethyl ester, (methyl) acrylic acid N, N-diethylamino methyl ester, (methyl) acrylic acid N, N-dimethyl aminoethyl ester, (methyl) acrylic acid N, N-diethylamino ethyl ester, (methyl) acrylic acid N, N-dimethylamino butyl ester, (methyl) acrylic acid N, N-diethylamino butyl ester, (methyl) acrylic acid N, N-dimethylamino hexyl ester, (methyl) acrylic acid N, N-dimethylamino octyl group ester, (methyl) acrylic acid N, N-dimethylamino dodecyl ester, N-[3-(dimethylamino) propyl group] Methacrylamide, N-[3-(dimethylamino) propyl group] acrylamide, N-[3-(dimethylamino) butyl] Methacrylamide, N-[8-(dimethylamino) octyl group] Methacrylamide, N-[12-(dimethylamino) dodecyl] Methacrylamide, N-[3-(diethylamino) propyl group] Methacrylamide, N-[3-(diethylamino) propyl group] acrylamide;
Maleic acid, fumaric acid, maleic anhydride and its half ester, .beta.-methylacrylic acid, itaconic acid, diallyldimethylammonium chloride, vinyl ethers (for example: methyl, ethyl, butyl or dodecyl vinyl), methyl vinyl ketone, maleimide, vinylpyridine, vinyl imidazole, vinyl furan, styrene, sulfonic acid styrene esters, 1-propenol-3 and its mixture.
In the middle of these, preferred especially acrylic acid, methacrylic acid, maleic acid, fumaric acid .beta.-methylacrylic acid, maleic anhydride and its half ester, acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-BMA, tert-butyl acrylate, metering system tert-butyl acrylate, Isobutyl 2-propenoate, isobutyl methacrylate, 2-ethylhexyl acrylate, stearyl acrylate base ester, the methacrylic acid stearyl, N tert butyl acrylamide, N-octyl acrylamide, acrylic acid 2-hydroxyethyl ester, the acrylic acid hydroxypropyl ester, methacrylic acid 2-hydroxyl ethyl ester, hydroxypropyl methacrylate, (methyl) acrylic acid alkylidene diol ester, styrene, unsaturated sulfonic acid such as acrylamido propane sulfonic acid, vinyl ethers is (as methyl, ethyl, butyl or dodecyl vinyl), 1-vinyl-glyoxal ethyline, methacrylic acid N, N-dimethylaminomethyl ester and N-[3-(dimethylamino) propyl group] Methacrylamide; Chlorination 3-methyl isophthalic acid-vinyl imidazole, methylsulfuric acid 3-methyl isophthalic acid-vinyl imidazole, methacrylic acid N, N-dimethyl aminoethyl ester is with chloromethanes, Methylsulfate or the quaternised N-[3-of dithyl sulfate (dimethylamino) propyl group] Methacrylamide.
Having the monomer of basic nitrogen atom here, can be quaternized in the following manner:
What be suitable for quaternized amine is the alkyl halide that for example contains 1-24 carbon atom in alkyl, as chloromethanes, and Celfume, iodomethane, ethyl chloride, bromoethane, chloropropane, hexyl chloride, dodecyl chloride, lauryl chloride and benzyl halogenide, particularly benzyl chloride and benzyl bromide a-bromotoluene.Suitable in addition quaternizing agent is sulphuric acid dialkyl, particularly dimethyl sulfate or dithyl sulfate.The quaternization of basic amine also can be in the presence of acid carries out with oxyalkylene such as ethylene oxide or propylene oxide.Preferred quaternizing agent is: chloromethanes, dimethyl sulfate or dithyl sulfate.
Quaternization can carry out before or after polymerization.
In addition, can also use unsaturated acids, for example the quaternized chloropropylene oxide (R of acrylic or methacrylic acid and following general formula (X) 31=C 1-C 40Alkyl) product.
Therefore, the example for example is: (methyl) acryloxy hydroxypropyl-trimethyl ammonium chloride and (methyl) acryloxy hydroxypropyl triethyl ammonium chloride.
The alkalescence monomer also can pass through with mineral acid such as sulphuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid, or neutralizes and cationization with organic acid such as formic acid, acetic acid, lactic acid or citric acid.
Suitable monomers (D) is the open chain N-vinylamide chemical compound of general formula (I) in addition:
Figure A0382318500092
Wherein: R 1, R 2, R 3=H or C 1-C 6Alkyl, and
Open chain N-vinylamide chemical compound for example is the N-vinyl formamide, N-vinyl-N-methylformamide, the N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl acrylamide, N-vinyl-N-methyl propanamide and N-vinyl butyramide.In this group monomer, preferably use the N-vinyl formamide.
Suitable monomers (D) also has acrylic acid polyester ether in addition, and for the purpose of the present invention, they are interpreted as referring to α usually, the unsaturated list of β-olefinic-and the ester of dicarboxylic acids and Aethoxy Sklerol.Suitable Aethoxy Sklerol is linearity that contains ehter bond or the branched substances with terminal hydroxy group.In general, their molecular weight is about 150-20000.Suitable Aethoxy Sklerol is a poly alkylene glycol, as Polyethylene Glycol, and polypropylene glycol, PolyTHF and oxyalkylene copolymers.The suitable oxyalkylene that is used to prepare oxyalkylene copolymers is an ethylene oxide for example, propylene oxide, chloropropylene oxide, 1,2-and 2,3-butylene oxide.Described oxyalkylene copolymers can contain the copolyalkylene oxide unit that is the random distribution form or is block form.Preferred ethylene oxide/propylene oxide copolymer.Preferred monomer D is the acrylic acid polyester ether of general formula I I:
Figure A0382318500101
Wherein:
The order of oxyalkylene units is arbitrarily,
K and l are the integer of 0-500 independently of one another, and wherein the summation of k and l is at least 5,
R 5Be hydrogen or C 1-C 8Alkyl and
R 6Be hydrogen or C 1-C 18Alkyl,
Y is O or NR 7, R wherein 7Be hydrogen, C 1-C 8Alkyl or C 5-C 8Cycloalkyl.
Preferably, k is the integer of the integer of 1-500, particularly 3-250.Preferably, l is the integer of 0-100.
Preferably, R 5Be hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl or n-hexyl, particularly hydrogen, methyl or ethyl.
Preferably, the R among the formula II 6Be hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, n-pentyl, n-hexyl, octyl group, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl.
Preferably, the Y among the formula II is O or NH.
Suitable acrylic acid polyester ether is for example above-mentioned α, the polycondensation product of unsaturated list of β-olefinic and/or dicarboxylic acids and acyl chlorides, amide and anhydride and Aethoxy Sklerol.Suitable Aethoxy Sklerol can be at an easy rate by making ethylene oxide, 1,2-propylene oxide and/or chloropropylene oxide and starter molecules such as water or short chain alcohol R 6-OH reaction makes.Described oxyalkylene can use separately, alternately use in succession or use with the form of mixture.Acrylic acid polyester ether can be separately or is used to prepare polymer used according to the invention with the form of mixture.
Operable cross-linking monomer (D) is the chemical compound with at least two ethylenical unsaturated double bonds, such as the ester of ethylenically unsaturated carboxylic acids such as acrylic or methacrylic acid and polyhydric alcohol, the ether of the alcohol of binary such as vinyl ethers or allyl ether at least.
The example of parent alcohol is a dihydroxylic alcohols, as 1, and 1, the 2-propylene glycol, 1, ammediol, 1,2-butanediol, 1, the 3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-ene-1,4-glycol, 1,2-pentanediol, 1, the 5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, decamethylene-glycol, 1,2-dodecanediol, 1, the 12-dodecanediol, neopentyl glycol, 3-methylpentane-1,5-glycol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1, the 2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-two (methylol) cyclohexane extraction, monohydroxy neopentanoic acid DOPCP, 2,2-two (4-hydroxyphenyl) propane, 2,2-two [4-(2-hydroxypropyl) phenyl] propane, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), dipropylene glycol, tripropylene glycol, four propylene glycol, 3-sulfo-pentane-1,5-two pure and mild Polyethylene Glycol, polypropylene glycol and PolyTHF, back three's molecular weight is 200-10000.Except the homopolymer of ethylene oxide and/or propylene oxide, can also use the block copolymer of ethylene oxide or propylene oxide or contain the ethylene oxide that is the introducing form and the copolymer of propylene oxide group.The example that has more than the parent alcohol of two OH groups is a trimethylolpropane, glycerol, and tetramethylolmethane, 1,2,5-penta triol, 1,2, the 6-hexanetriol, the triethoxy cyanuric acid, sorbitan, sugar is as sucrose, glucose, mannose.Undoubtedly, polyhydric alcohol can also be after itself and ethylene oxide or propylene oxide reaction respectively with the form use of corresponding ethoxylate or propoxylate.Polyhydric alcohol also can be at first by being converted into corresponding glycidyl ether with the chloropropylene oxide reaction.
Suitable crosslinking agent is vinyl esters or monobasic unsaturated alcohol and the unsaturated C of olefinic in addition 3-C 6Carboxylic acid is as the ester of acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.The example of this class alcohol is a 1-propenol-3,1-butylene-3-alcohol, 5-hexen-1-ol, 1-octene-3-alcohol, 9-decen-1-ol, two cyclopentenols, 10-undecene-1-alcohol, cinnamyl alcohol, citronellol, crotonyl alcohol. or cis-9-vaccenic acid-1-alcohol.But, can also use polybasic carboxylic acid such as malonic acid, tartaric acid, trimellitic acid, phthalic acid, p-phthalic acid, citric acid or succinic acid with the esterification of monobasic unsaturated alcohol.
Suitable crosslinking agent is a unsaturated carboxylic acid in addition, for example the ester of oleic acid .beta.-methylacrylic acid, cinnamic acid or 10-9-undecylenic acid and above-mentioned polyhydric alcohol.
Suitable straight chain or branching, linear or cyclic aliphatic series or the aromatic hydrocarbon that has at least two two keys in addition, under the situation of aliphatic hydrocarbon, must not conjugated, as divinylbenzene, divinyl toluene, 1, the 7-octadiene, 1, the 9-decadinene, 4-vinyl-1-cyclohexene, trivinyl cyclohexane extraction or molecular weight are the polybutadiene of 200-20000.
Suitable unsaturated carboxylic acid in addition, as acrylic acid and methacrylic acid, itaconic acid, the amide of maleic acid and the N-allylamine that is at least dual functional amine, for example 1,2-diaminourea methane, 1,2-diaminoethanes, 1,3-diaminopropanes, 1,4-diaminobutane, 1,6-diamino hexane, 1, the N-allylamine of 12-dodecane diamidogen, piperazine, diethylenetriamines or isophorone diamine.Same suitable also have allylamine and unsaturated carboxylic acid are as the amide of the carboxylic acid of acrylic acid, methacrylic acid, itaconic acid, maleic acid or aforesaid binary at least.
In addition, triallylamine or corresponding ammonium salt also are suitable for as cross-linking agent as triallyl ammonio methacrylate or methylsulfuric acid triallyl ammonium methyl.
In addition, can use the N-vinyl compound of urea derivative, dual functional at least amide, cyanurate or urethane, the N-vinyl compound of urea, ethylidene-urea, propylidene urea or winestone diamides for example is as N, N '-divinyl ethylidene-urea or N, N '-divinyl propylidene urea.
Suitable crosslinking agent is the divinyl diox in addition, tetraallyl silane or tetrem thiazolinyl silane.
Particularly preferred cross-linking agent is a methylene diacrylamine for example, divinylbenzene, triallylamine and tetraallyl ammonium salt, the divinyl imidazoles, N, N '-divinyl ethylidene-urea, the product of polyhydric alcohol and acrylic or methacrylic acid, with ethylene oxide and/or propylene oxide and/or the polyalkylene oxides of chloropropylene oxide reaction or the methacrylate and the acrylate of polyhydric alcohol, and polyhydric alcohol is as 1,2-ethylene glycol, 1, the 4-butanediol, diethylene glycol, trimethylolpropane, glycerol, tetramethylolmethane, sorbitan and sugar are as sucrose, glucose, the allyl ether of mannose or vinyl ethers.
Cross-linking agent very particularly preferably is a pentaerythritol triallyl ether, sugar is as the allyl ether of sucrose, glucose and mannose, divinylbenzene, methylene diacrylamine, N, (methyl) acrylate of N '-divinyl ethylidene-urea and ethylene glycol, butanediol, trimethylolpropane or glycerol or with (methyl) acrylate of ethylene glycol, butanediol, trimethylolpropane or the glycerol of the reaction of ethylene oxide and/or chloropropylene oxide.
The content of monomer (D) is 0-10 weight %, preferred 0-5 weight %, preferred especially 0-2 weight %.
Polymer (E) is preferably selected from:
E1) contain the chemical compound of polyethers,
E2) contain the unitary polymer of the vinyl pyrrolidone that is copolymerized form of at least 5 weight %,
E3) contain the polymer of the vinyl alcohol units of at least 50 weight %,
E4) contain the natural materials of carbohydrate structure.
As the compd E 1 that contains polyethers), can use based on ethylene oxide, propylene oxide, butylene oxide and other oxyalkylene, the perhaps polyalkylene oxides of polyglycereol.According to the unitary type of monomer structure, this polymer contains following construction unit:
-(CH 2) 2-O-，-(CH 2) 3-O-，-(CH 2) 4-O-，-CH 2-CH(R 9)-O-，-CH 2-CHOR 10-CH 2-O-
Wherein:
R 9Be C 1-C 24Alkyl;
R 10Be hydrogen, C 1-C 24Alkyl, R 9-C (=O)-, R 9-NH-C (=O)-.
Here, described construction unit can be a homopolymer, or random copolymer and block copolymer.
As polymer (E), preferably use the polymer of the general formula I I of molecular weight＞300:
Wherein each variable has following implication independently of one another:
R 4Be hydrogen, C 1-C 24Alkyl, R 9-C (=O)-, R 9-NH-C (=O)-, the polyhydric alcohol group;
R 8Be hydrogen, C 1-C 24Alkyl, R 9-C (=O)-, R 9-NH-C (=O)-;
R 5-R 7Be-(CH 2) 2-,-(CH 2) 3-,-(CH 2) 4-,-CH 2-CH (R 9)-,-CH 2-CHOR 10-CH 2-;
R 9Be C 1-C 24Alkyl;
R 10Be hydrogen, C 1-C 24Alkyl, R 9-C (=O)-, R 9-NH-C (=O)-;
A is-C (=O)-O ,-C (=O)-B-C (=O)-O ,-C (=O)-NH-B-NH-C (=O)-O;
B is-(CH 2) t-, arlydene, its optional being substituted;
N is 1-1000;
S is 0-1000;
T is 1-12;
U is 1-5000;
V is 0-5000;
W is 0-5000:
X is 0-5000;
Y is 0-5000;
Z is 0-5000.
Here, be that the terminal primary hydroxyl of the basic polyethers for preparing and the secondary OH group of polyglycereol can exist so that unprotected form is free with the polyalkylene oxides, be C with chain length respectively perhaps 1-C 24Alcohol or chain length be C 1-C 24Carboxylic acid etherificate or esterification, perhaps form urethane with isocyanate reaction.
The R that can mention 4And R 8-R 10Alkyl be branching or nonbranched C 1-C 24Alkyl chain, preferable methyl, ethyl, n-pro-pyl, the 1-Methylethyl, normal-butyl, the 1-methyl-propyl, the 2-methyl-propyl, 1, the 1-dimethyl ethyl, n-pentyl, the 1-methyl butyl, the 2-methyl butyl, the 3-methyl butyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, n-hexyl, 1, the 1-dimethyl propyl, 1, the 2-dimethyl propyl, the 1-methyl amyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 1-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 2, the 3-dimethylbutyl, 3, the 3-dimethylbutyl, the 1-ethyl-butyl, the 2-ethyl-butyl, 1,1,2-trimethyl propyl group, 1,2,2-trimethyl propyl group, 1-ethyl-1-methyl-propyl, 1-ethyl-2-methyl-propyl, n-heptyl, the 2-ethylhexyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl, the n-tridecane base, the n-tetradecane base, the Pentadecane base, n-hexadecyl, the n-heptadecane base, the n-octadecane base, AI3-36122 base or AI3-28404 base.
The preferred representative of the abovementioned alkyl that can mention is branching or nonbranched C 1-C 12Alkyl chain, preferred especially C 1-C 6Alkyl chain.
The molecular weight of polyethers is preferably 300-100000 greater than 300 (number averages), preferred especially 500-50000, especially preferred 800-40000.
Advantageously, use the homopolymer of ethylene oxide or ethylene oxide content copolymer as 40-99 weight %.For the ethylene oxide polymer of preferred use, therefore the content of the ethylene oxide of copolymerization be 40-100 mole %.The suitable comonomer that is used for these copolymers is a propylene oxide, butylene oxide and/or oxidation isobutene..The copolymer of ethylene oxide and propylene oxide for example, the copolymer of the copolymer of ethylene oxide and butylene oxide and ethylene oxide, propylene oxide and at least a butylene oxide is suitable.The content of ethylene oxide is preferably 40-99 mole % in the copolymer, and the content of propylene oxide is preferably 1-60 mole %, and the content of butylene oxide is preferably 1-30 mole %.Except that straight chain homopolymer or copolymer, can also use the homopolymer or the copolymer of branching.
Branched polymer can pass through ethylene oxide and suitable, also have propylene oxide and/or butylene oxide for example to add on polyhydric alcohol group such as tetramethylolmethane, the glycerol, perhaps add on sugar alcohol such as D-Sorbitol and the D-mannitol, and add on polysaccharide such as cellulose and the starch and prepare.Oxyalkylene units can be present in the polymer with the form of random distribution or the form of block.
But, also can use molal weight to be the polyalkylene oxides of 1500-25000 and the polyester of aliphatic series or aromatic dicarboxylic acid such as oxalic acid, succinic acid, adipic acid and p-phthalic acid, as among the EP-A-0 743962 as containing as described in the chemical compound of polyethers.In addition, can also use by making Merlon that polyalkylene oxides and phosgene or carbonic ester such as diphenyl carbonate reaction obtain and by making polyalkylene oxides and aliphatic series and aromatic diisocyanates react the polyurethane that obtains.
As polyethers (E), preferred especially mean molecule quantity is the polymer of the general formula I I of 300-100000 (number average), and wherein each variable has following implication independently of one another:
R 4Be hydrogen, C 1-C 12Alkyl, R 9-C (=O)-, R 9-NH-C (=O)-, the polyhydric alcohol group;
R 8Be hydrogen, C 1-C 12Alkyl, R 9-C (=O)-, R 9-NH-C (=O)-;
R 5-R 7Be-(CH 2) 2-,-(CH 2) 3-,-(CH 2) 4-,-CH 2-CH (R 9)-,-CH 2-CHOR 10-CH 2-;
R 9Be C 1-C 12Alkyl;
R 10Be hydrogen, C 1-C 12Alkyl, R 9-C (=O)-, R 9-NH-C (=O)-;
N is 1-8;
S is 0;
U is 2-2000;
V is 0-2000;
W is 0-2000.
Especially preferred polyethers is that mean molecule quantity is the polymer of the general formula I I of 500-50000 (number average), and wherein each variable has following implication independently of one another:
R 4Be hydrogen, C 1-C 6Alkyl, R 9-C (=O)-, R 9-NH-C (=O)-;
R 8Be hydrogen, C 1-C 6Alkyl, R 9-C (=O)-, R 9-NH-C (=O)-;
R 5-R 7Be-(CH 2) 2-,-(CH 2) 3-,-(CH 2) 4-,-CH 2-CH (R 9)-,-CH 2-CHOR 10-CH 2-;
R 9Be C 1-C 6Alkyl;
R 10Be hydrogen, C 1-C 6Alkyl, R 9-C (=O)-, R 9-NH-C (=O)-;
N is 1;
S is 0;
U is 5-500;
V is 0-500;
W is 0-500.
In addition, operable polyethers (E1) contains the homopolymer and the copolymer of the ethylenically unsaturated monomer of polyalkylene oxides in addition, as the homopolymer and the copolymer of polyalkylene oxides (methyl) acrylate, polyalkylene oxides vinyl ethers, polyalkylene oxides (methyl) acrylamide, polyalkylene oxides pi-allyl amide or polyalkylene oxides vinylamide.Certainly, also can use the copolymer of this class monomer and other ethylenically unsaturated monomer.
Yet the operable chemical compound (E1) that contains polyethers can also be the product of polymine and oxyalkylene.In this case, the preferred ethylene oxide of the oxyalkylene of use, propylene oxide, butylene oxide and its mixture, preferred especially ethylene oxide.The polymine of using can be that number-average molecular weight is 300-20000, preferred 500-10000, the polymer of preferred especially 500-5000.The oxyalkylene that uses and the weight ratio of polymine are 100: 1-0.1: 1, preferred 50: 1-0.5: 1, preferred especially 20: 1-0.5: 1.
But, contain the unitary polymer E2 of at least 5 weight % vinyl pyrrolidones) also can be used as polymer (E).These polymer preferably contain the vinyl pyrrolidone of at least 10 weight %, the vinyl pyrrolidone of preferred especially at least 30 weight %.
The suitable vinyl pyrrolidone comonomer that is used for synthetic polymer (E2) is a N-caprolactam for example, the N-vinyl imidazole, N-vinyl-glyoxal ethyline, N-vinyl-4-methylimidazole, chlorination 3-methyl isophthalic acid-vinyl imidazole, methylsulfuric acid 3-methyl isophthalic acid-vinyl imidazole, diallyl ammonium chloride, styrene, ring-alkylated styrenes.
The other suitable comonomer that is used to prepare polymer (E3) is that for example monoene belongs to unsaturated C 3-C 6Carboxylic acid, as acrylic acid, methacrylic acid, .beta.-methylacrylic acid, fumaric acid and ester thereof, amide and nitrile, such as acrylic acid methyl ester., ethyl acrylate, methyl methacrylate, ethyl methacrylate, the methacrylic acid stearyl, hydroxyethyl acrylate, the acrylic acid hydroxypropyl ester, hydroxybutyl acrylate, hydroxyethyl methylacrylate, hydroxypropyl methacrylate, acrylic acid hydroxyl isobutyl, the hydroxyethyl methacrylate isobutyl, monomethyl maleate, dimethyl maleate, ethyl maleate, ethyl maleate., 2-ethylhexyl acrylate, methacrylic acid 2-ethyl hexyl ester, maleic anhydride and its half ester, (methyl) acrylic acid alkylidene diol ester, acrylamide, Methacrylamide, the N-DMAA, N tert butyl acrylamide, acrylonitrile, methacrylonitrile, vinyl ethers such as methyl, ethyl, butyl or dodecyl vinyl, cationic monomer is as (methyl) propenoic acid dialkyl aminoalkyl ester and dialkyl aminoalkyl (methyl) acrylamide, as acrylic acid dimethyl aminoethyl ester, and acrylic acid diethylamino ethyl ester, the salt of methacrylic acid diethylamino ethyl ester and above-mentioned monomer and carboxylic acid or mineral acid, and quaternized products.
Polymer (E) prepares by known method, for example uses the solution, precipitation, suspension or the emulsion polymerization that form the chemical compound of free radical under polymerizing condition.Normally 30-200 ℃ of polymerization temperature, preferred 40-110 ℃.Suitable initiator is for example azo and per-compound, and redox initiator system commonly used, such as the combination of hydrogen peroxide and reproducibility chemical compound such as sodium sulfite, sodium sulfite, sodium sulfoxylate formaldehyde and hydrazine.Suitable, these systems can also comprise a spot of heavy metallic salt in addition.
The K value of homopolymer and copolymer (polymer E2) is at least 7, preferred 10-250.But the K value of described polymer can be no more than 300.This K value is according to H.Fikentscher, Cellulose-Chemie (cellulose chemistry), and the 13rd volume, the method among 58-64 and the 71-74 (1932) is measured under 25 ℃ in aqueous solution, depends on K value scope, measures concentration between 0.1%-5%.
But the polymer (E3) that contains at least 50 weight % vinyl alcohol units also can be used as polymer (E).Preferably, this base polymer contains at least 70 weight %, the polyvinyl alcohol units of preferred especially 80 weight %.This base polymer is normally by with the vinyl esters polymerization, and proceeds to subsequently that small part alcoholysis, aminolysis or hydrolysis prepare.The C of preferred linearity and branching 1-C 12The vinyl esters of carboxylic acid, preferred especially vinylacetate.Undoubtedly, vinyl esters also can use with the form of mixture.
The suitable vinyl esters comonomer that is used for synthetic polymer (E3) is a N-caprolactam for example, the N-vinyl pyrrolidone, the N-vinyl imidazole, N-vinyl-glyoxal ethyline, N-vinyl-4-methylimidazole, chlorination 3-methyl isophthalic acid-vinyl imidazole, methylsulfuric acid 3-methyl isophthalic acid-vinyl imidazole, diallyl ammonium chloride, styrene, ring-alkylated styrenes.
The other suitable comonomer that is used to prepare polymer (E3) is that for example monoene belongs to unsaturated C 3-C 6Carboxylic acid, as acrylic acid, methacrylic acid, .beta.-methylacrylic acid, fumaric acid and ester thereof, amide and nitrile, such as acrylic acid methyl ester., ethyl acrylate, methyl methacrylate, ethyl methacrylate, the methacrylic acid stearyl, hydroxyethyl acrylate, the acrylic acid hydroxypropyl ester, hydroxybutyl acrylate, hydroxyethyl methylacrylate, hydroxypropyl methacrylate, acrylic acid hydroxyl isobutyl, the hydroxyethyl methacrylate isobutyl, monomethyl maleate, dimethyl maleate, ethyl maleate, ethyl maleate., 2-ethylhexyl acrylate, methacrylic acid 2-ethyl hexyl ester, maleic anhydride and its half ester, (methyl) acrylic acid alkylidene diol ester, acrylamide, Methacrylamide, the N-DMAA, N tert butyl acrylamide, acrylonitrile, methacrylonitrile, vinyl ethers such as methyl, ethyl, butyl or dodecyl vinyl, cationic monomer is as (methyl) propenoic acid dialkyl aminoalkyl ester and dialkyl aminoalkyl (methyl) acrylamide, as acrylic acid dimethyl aminoethyl ester, and acrylic acid diethylamino ethyl ester, the salt of methacrylic acid diethylamino ethyl ester and above-mentioned monomer and carboxylic acid or mineral acid, and quaternized products.
Preferably, polymer (E3) is by making the vinylacetate homopolymerization, and proceeds to the polymer of small part hydrolysis, alcoholysis or aminolysis preparation subsequently.
Polymer (E3) prepares by known method, for example uses the solution, precipitation, suspension or the emulsion polymerization that form the chemical compound of free radical under polymerizing condition.Normally 30-200 ℃ of polymerization temperature, preferred 40-110 ℃.Suitable initiator is for example azo and per-compound, and redox initiator system commonly used, such as the combination of hydrogen peroxide and reproducibility chemical compound such as sodium sulfite, sodium sulfite, sodium sulfoxylate formaldehyde and hydrazine.Suitable, these systems can also comprise a spot of heavy metallic salt in addition.
In order to prepare polymer (E3), with original monomer and suitable, monomeric ester group in addition proceeds to the small part cracking by hydrolysis, alcoholysis or aminolysis after polymerization.Hereinafter, this processing step is referred to as saponification.Saponification, is preferably undertaken by adding sodium hydroxide or potassium hydroxide aqueous solution and/or alcohol by adding alkali or acid by known mode own.Especially preferably use the methanol solution of sodium hydroxide or potassium hydroxide.Carrying out saponified temperature range is 10-80 ℃, preferred 20-60 ℃.Saponification degree depends on the water content of consumption, saponification temperature, saponification time and the solution of alkali or acid.
Particularly preferred polymer (E3) is by making the vinylacetate homopolymerization, and proceeds to the polymer of small part saponification preparation subsequently.This class contains the polymer of polyvinyl alcohol units can trade name Mowiol Obtain.Yet,, also can use the natural materials (E4) that contains carbohydrate structure as polymer (E).This class natural materials is the saccharide of for example plant or animal origin or product and its catabolite that is formed by microbial metabolism.Suitable polymers (E4) is an oligosaccharide for example, polysaccharide, but the polysaccharide of oxidation-degradable enzymatically degrading or hydrolyzable degraded, the polysaccharide of oxidable hydrolytic degradation or oxidable enzymatically degrading, the oligosaccharide of chemical modification or polysaccharide and composition thereof.
Preferred product is US 5,334, the chemical compound of mentioning in 20 row-Di, 5 hurdles, 287 the 4th hurdles, 45 row.
As monomer E and D, preferably use water solublity or water dispersible monomer, the preferred water soluble monomers.Water solublity is interpreted as referring to that monomer down can be soluble in water with the amount of at least 2 weight % at 25 ℃.
Described polymer is the radical polymerization preparation by monomer A-D, and is suitable, in the presence of polymer E.This method is for example undertaken by precipitation, suspension, emulsion, solution or dispersin polymerization and bulk polymerization under polymerizing condition commonly used.In water or in organic solvent, normally in alcohol or in water/alcohol mixture, carry out polymerisation in solution and be proved to be particularly advantageous.Here, this method is carried out under 60-130 ℃ temperature usually, and wherein this reaction can be carried out under atmospheric pressure, self-generated pressure or decompression.
The initiator that can be used for radical polymerization is water solublity and water-insoluble peroxide and/or the azo-compound that is usually used in this purpose, for example alkali metal peroxydisulfate or peroxy-disulfuric acid ammonium salt, dibenzoyl peroxide, cross neopentanoic acid tertiary butyl ester, mistake-2 ethyl hexanoic acid tertiary butyl ester, di-t-butyl peroxide, t-butyl hydroperoxide, azodiisobutyronitrile, azo two (2-amidine propane) dihydrochloride or 2,2 '-azo two (2-methylbutyronitrile).Suitable initiator mixture or redox initiator system in addition, such as ascorbic acid/iron sulfate (II)/sodium persulfate, t-butyl hydroperoxide/sodium dithionite, t-butyl hydroperoxide/hydroxyl methane sulfinic acid sodium.Initiator can use with amount commonly used, for example based on the amount for the treatment of polymerization single polymerization monomer to be the amount use of 0.05-5 weight %.
The K value of polymer is between 10-350, preferred 20-200, and preferred especially 35-110 is especially between the 40-80.The K value is according to Fikentscher, Cellulosechemie, the 13rd volume, the method in the 58-64 page or leaf (1932) under 25 ℃ with the determination of aqueous solution of 1% concentration.
The selection of the amount of monomer and solvent should advantageously make the copolymer solution that obtains 20-80 weight % concentration.At first, in reaction vessel, polymer E is incorporated in the water with dissolving, swelling or dispersive form, adds monomer afterwards, preferably use 3-70 weight % concentration, the particularly mixture of 3-50 weight % concentration.
Suitable, make polymeric blends carry out other post polymerization and suitable, handle by steam distillation, with acid/alkali or oxidation or Reducing agent and carry out post processing.In preferred embodiments, polymer is carried out steam distillation.
For stable, use Euxyl K 100 (Sch ü lke ﹠amp; Mayr), Phenonip (Clariant) or alternative stabilizing agent polymer solution is handled.
By precipitation, spray drying or lyophilizing can obtain powdered product from proper solvent system.
Described gel with the film former preparation is characterised in that comparing with prior art has the performance of improvement.
Polymer of the present invention can be advantageously used in the cosmetic formulations, in the hair cosmetic preparation.
Broad understanding answered in term " cosmetic formulations " is to refer to that all are applicable to skin and/or hair and/or fingernail and seek those preparations of non-pure therapeutic treatment purpose.
Polymer of the present invention can be used in the cosmetics for skin preparation.
For example, polymer of the present invention is used for the cosmetic composition that cleaning skin is used.This type of cosmetic cleaning composites is selected from: soap slab, and as fancy soap, curd soap, transparent soap, senior fancy soap, deodorant soap, the cream soap, baby's soap, skin protection soap, abrasive soap and synthectic detergents, liquid soap is as paste soap, soft soap and cleaning paste, liquid scrubbing, shower and bath preparation, as washing liquid, body lotion and shower gels, foam bath, oil bath and scouring preparation.
Preferred polymer of the present invention is used for the cosmetic composition of nursing and protecting skin to use, and is used for the neutralization of fingernail care composition and is used to modification property cosmetic formulations.
Be particularly preferred for skin care compositions and methods, the privacy care composition protects sufficient compositions, deodorant, photoprotection compositions, repellant, the compositions of having a shave, Depilatory composition, anti-acne compositions, cosmetics, mascara, lipstick, eye shadow, eye shadow brush, eyeliner, rouge, cosmetics and eyebrow pencil.
Skin care compositions and methods especially is water-in-oil type or oil-in-water type protective skin cream, day cream and late frost, eye cream, facial cream, anti-wrinkle cream, emollient cream, fair complexion cream, vitamins cream, moisturizer, the form of nursing emulsion and moisturizing emulsion.
Polymer of the present invention can produce special effect in cosmetic formulations.This polymer especially can help the moistening and the conditioning of skin and the improvement that helps skin feel.This polymer can also be used as thickening agent in preparaton.The interpolation of polymer of the present invention can cause sizable improvement aspect skin-friendliness in some preparaton.
The amount of copolymer of the present invention in the cosmetics for skin preparation is about 0.001-20 weight % based on the gross weight of compositions, preferred 0.01-10 weight %, very particularly preferably 0.1-5 weight %.
Depend on application, the present composition can be to be suitable for the form of skin nursing, for example with cream, and foam, gel, rod, powder, mousse, Emulsion or emulsion form are used.
Except that polymer of the present invention and suitable solvent, the cosmetics for skin preparation can also comprise additive commonly used in the cosmetics, as emulsifying agent, antiseptic, aromatic oil, cosmetic active ingredient, as phytantriol, vitamin A, E and C, retinol, bisabolol, pantothenylol, light protective agent, bleach, coloring agent, toner, suntan (for example dihydroxyacetone), collagen, protein hydrolysate, stabilizing agent, pH regulator agent, dyestuff, salt, thickening agent, gel former, bodying agent, polysiloxanes, wetting agent, fatting agent and other typical additives again.
Suitable solvent is water and low-grade monobasic alcohol or polyhydric alcohol or its mixture with 1-6 carbon atom especially; Preferred monohydric alcohol or polyhydric alcohol are ethanol, isopropyl alcohol, propylene glycol, glycerol and Sorbitol.
Other typical additives that can exist is a fat-body, as mineral oil and artificial oil, and alkane for example, silicone oil and have the aliphatic hydrocarbon that surpasses 8 carbon atoms, animal oil and vegetable oil, sunflower oil for example, Oleum Cocois, American Avocado Tree oil, olive oil, lanoline, or wax, fatty acid, fatty acid ester, for example C 6-C 30The triglyceride of fatty acid, wax ester, for example Jojoba oil, aliphatic alcohol, vaseline, hydrogenated lanolin and acetylated lanolin.Certainly also can use their mixture.
Customary thickeners in these preparatons is crosslinked acrylic acid series polymeric compounds and derivant thereof, polysaccharide, as HANSHENGJIAO, agar, alginate or tylose, carboxymethyl cellulose or hydroxyl carboxymethyl cellulose, aliphatic alcohol, one acid glyceride and fatty acid, polyvinyl alcohol and polyvinyl pyrrolidone.
Set specific performance properties if desired, polymer then of the present invention can also mix with conventional polymer.
The example of suitable conventional polymer is an anionic polymer, cationic polymer, amphiphilic polymers and neutral polymer.
The example of anionic polymer is the homopolymer and the copolymer of acrylic acid and methacrylic acid or its salt, the copolymer of acrylic acid and acrylamide and salt thereof; Multi-hydroxy carboxy acid's sodium salt, water solublity or water-dispersible polyester, polyurethane and polyureas.Specially suitable polymer is the copolymer (Luvimer for example of tert-butyl acrylate, acrylic acid ethyl ester, methacrylic acid 100P), the copolymer of acrylic acid ethyl ester and methacrylic acid (Luvimer for example MAE), N tert butyl acrylamide, acrylic acid ethyl ester, acrylic acid copolymer (Ultrahold 8, strong), vinyl acetate .beta.-methylacrylic acid and suitable, the copolymer of other vinyl esters (Luviset for example Each grade), copolymer-maleic anhydride (optional with alcohol reaction), anion polysiloxane (for example carboxy-functionalized those), the copolymer of vinyl pyrrolidone, tert-butyl acrylate, methacrylic acid (Luviskol for example VBM), acrylic acid and methacrylic acid and hydrophobic monomer (methyl) acrylic acid C for example 4-C 30Arrcostab, C 4-C 30Alkyl vinyl ester, C 4-C 30Alkyl vinyl ether and hyaluronic copolymer.
Other suitable polymers is the cationic polymer with INCI title Polyquaternium, for example copolymer (the Luviquat of vinyl pyrrolidone/N-vinyl imidazole salt FC, Luviquat HM, Luviquat MS, Luviquat Care), use the copolymer (Luviquat of the quaternised N-vinyl pyrrolidone of dithyl sulfate/dimethylaminoethyl acrylate methyl base amino-ethyl ester PQ 11), the copolymer (Luviquat of N-caprolactam/N-vinyl pyrrolidone/N-vinyl imidazole salt Hold); Cationic cellulose derivative (Polyquaternium-4 (hydroxyethyl-cellulose/diallyldimethylammonium chloride copolymer) and Polyquaternium-10), acrylamide copolymer (Polyquaternium-7 (polyquaternary ammonium salt of acrylamide and dimethyl diallyl ammonium chloride system)) and chitosan.
Other suitable polymer also has neutral polymer, as the polyvinyl pyrrolidone class, the copolymer of N-vinyl pyrrolidone and vinyl acetate and/or vinyl propionate base ester, polysiloxanes, Vinylcaprolactam homopolymer and contain the N-vinylpyrrolidone copolymers, polymine and salt thereof, polyvinylamine and salt thereof, cellulose derivative, polyaspartic acid salts and derivant.
In order to produce some performance, preparation can additionally comprise the conditioning material based on polysiloxane compound.Suitable polysiloxane compound for example is poly-alkylsiloxane, poly-aryl siloxanes, poly-aryl alkyl siloxanes, polyether silicone or organic siliconresin.
Copolymer of the present invention is used for cosmetic formulations, and the latter produces according to the known common guidance of person skilled in the art.
This type of preparaton advantageously is emulsion form, preferably is Water-In-Oil (W/O) or oil-in-water (O/W) emulsion form.Yet, suitable according to the present invention, can also advantageously select the preparaton of other type, aqueous dispersion for example, gel, oil preparation, the oleogel agent, multi-phase emulsion for example is W/O/W or O/W/O emulsion, the form of anhydrous ointment or ointment base etc.
Can emulsion used according to the invention prepare by known method.
Except copolymer of the present invention, emulsion also comprises composition commonly used, as aliphatic alcohol, and the triglyceride of fatty acid ester, especially fatty acid, fatty acid, lanoline and derivant thereof, natural or synthetic oil or wax and the emulsifying agent in the presence of water.
Selection to the preparation of specific additive of emulsion type and suitable emulsion for example is described in Schrader, the ultimate principle and the prescription of Grundlagen und Rezepturen der Kosmetika[cosmetics], H ü thig Buch Verlag, Heidelberg, second edition, 1989, in the third part, the document is incorporated herein by reference in view of the above.
For example, protective skin cream that can be used according to the invention can be for example form of W/O emulsion.This class emulsion comprises water, this water utilize suitable emulsifier system be emulsified in oil phase or fat mutually in.
In this class emulsion, the concentration of emulsifier system is about 4-35 weight % based on the gross weight of emulsion; Fat accounts for about 20-60 weight % mutually and water accounts for about 20-70 weight %, under each situation all based on the gross weight of this emulsion.Emulsifying agent is to be generally used in this class emulsion those.They for example are selected from: C 12-C 18Sorbitan fatty acid esters; Hydroxy stearic acid and C 12-C 30The ester of aliphatic alcohol; C 12-C 18The monoesters of fatty acid and glycerol or polyglycereol and diester; The condensation substance of ethylene oxide and propylene glycol; The C of oxypropylation/oxyethylation 12-C 20Aliphatic alcohol; Multi-ring alcohol is as sterol; Has high-molecular weight aliphatic alcohol, as lanoline; The mixture of the pure and mild isostearic acid magnesium of oxypropylation/bound to polyglycerol; The succinate of polyoxyethyleneization or polyoxypropylene aliphatic alcohol; And the mixture of the lanoline hydrochlorate of magnesium, calcium, lithium, zinc or aluminum and hydrogenated lanolin or lanolin alcohol.
The suitable fat component of the fat that can be present in emulsion in mutually comprises hydrocarbon ils, as paraffin oil, and Purcellin l, perhydro-squalene and the microwax solution in these oil; Animal oil or vegetable oil, as Semen pruni armeniacae oil, American Avocado Tree oil, Calophylum l, lanoline and derivant thereof, Oleum Ricini, Oleum sesami, olive oil, Jojoba oil, candlenut oil, Hoplostethus l; The distillation starting point is that about 250 ℃ and distillation end point are 410 ℃ mineral oil, for example vaseline oil under atmospheric pressure; The ester of saturated and unsaturated fatty acid, as the myristic acid Arrcostab, for example isopropyl esters of myristic acid, butyl ester or cetyl ester, stearic acid cetyl ester, the ethyl ester of Palmic acid or isopropyl esters, the triglyceride and the ricinoleic acid cetyl ester of sad or capric acid.
Fat also can comprise the silicone oil that dissolves in other oil mutually, as dimethyl polysiloxane, methyl phenyl silicone and polysiloxanes-diol copolymer, and fatty acid and aliphatic alcohol.
In order to help the reservation of oil, also can use wax, Brazil wax for example, candelilla wax, Cera Flava, microwax, the oleate of ceresine and Ca, Mg and Al, myristate, linoleate and stearate.
In general, these water-in-oil emulsions by with fat mutually and emulsifying agent add in the mixer and prepare.Described container heats under 70-75 ℃ temperature, adds the oil-soluble composition then, and under agitation adds and be heated to same temperature and water soluble ingredient in advance and be dissolved in wherein water in advance; Stir this mixture, till obtaining to have the emulsion of required fineness, allow it be cooled to room temperature then, suitable, a little stirring.
In addition, nursing emulsion of the present invention can be the form of O/W emulsion.This emulsion comprises oil phase usually, makes oil phase be stabilized in the emulsifying agent and the water of aqueous phase, and it is the multiviscosisty form usually.
The suitable words of water of the O/W emulsion of preparation of the present invention comprise
-alcohol, glycol or polyhydric alcohol and ether thereof, preferred alcohol, isopropyl alcohol, propylene glycol, glycerol, ethylene glycol monoethyl ether;
-customary thickeners or gel former, for example crosslinked acrylic acid series polymeric compounds and derivant thereof, polysaccharide, as HANSHENGJIAO or alginate, carboxymethyl cellulose or hydroxyl carboxymethyl cellulose, aliphatic alcohol, polyvinyl alcohol and polyvinyl pyrrolidone.
Oil phase comprises oil ingredient commonly used in the cosmetics, for example:
-saturated and/or undersaturated branching and/or nonbranched C 3-C 30Alkanoic acid and saturated and/or undersaturated branching and/or nonbranched C 3-C 30The ester of alcohol, aromatic carboxylic acid and saturated and/or undersaturated branching and/or nonbranched C 3-C 30The ester of alcohol, myristic acid isopropyl esters for example, stearic acid isopropyl esters, stearic acid hexyl decyl ester, oleic acid oil base ester; And synthetic, the semi-synthetic and natural mixture of this type of ester, as Jojoba oil;
-branching and/or nonbranched hydrocarbon and chloroflo;
-silicone oil, as cyclomethicone, dimethyl polysiloxane, diethyl polysiloxanes, octamethylcy-clotetrasiloxane and composition thereof;
-dialkyl ether;
-mineral oil and mineral wax;
-saturated and/or undersaturated branching and/or nonbranched C 8-C 24The triglyceride of alkanoic acid; They can be selected from synthetic, semi-synthetic or natural oil, as olive oil, and Petiolus Trachycarpi oil, almond oil or mixture.
Suitable emulsifying agent is the O/W emulsifying agent preferably, as polyglycerin ester, and the glyceride of sorbitan ester or partial esterification.
Described preparation can be by melting oil phase down at about 80 ℃; Water soluble ingredient is dissolved in the hot water, and under agitation slowly joins in the oil phase; Carry out till mixture homogenization and being stirred to turned cold.
Polymer of the present invention also is suitable for washing and shower gels preparaton and bathes with in the preparation.
Except polymer of the present invention, this type of preparaton comprises usually as the anion surfactant of surface of base activating agent and as the both sexes and the non-ionic surface active agent of cosurfactant, and also has lipoid, aromatic oil, dyestuff, organic acid, antiseptic, antioxidant, thickening agent/gel former, skin conditioning agent and wetting agent.
With in the preparation, can use all aniones, neutrality, both sexes or the cationic surfactant that are generally used in the clean body compositions in washing, shower and bath.
Preparaton comprises 2-50 weight %, preferred 5-40 weight %, the surfactant of preferred especially 8-30 weight %.
Suitable anion surfactant for example is an alkyl sulfate, alkyl ether sulfate, alkylsulfonate; alkylaryl sulfonates, alkyl succinate, alkyl sulfo succinate; N-alkanoyl sarcosinate, acyl amino esilate, acyl-hydroxyethyl sulfonate; alkylphosphonic; alkyl ether phosphate, alkyl ether carboxy acid salt, alpha-alkene sulfonate; especially their alkali metal salt and alkali salt, for example sodium salt, potassium salt, magnesium salt, calcium salt and ammonium salt and triethanolamine salt.Alkyl ether sulfate, alkyl ether phosphate and alkyl ether carboxy acid salt can have 1-10 ethylene oxide or propylene oxide unit in molecule, preferred 1-3 ethylene oxide unit.
For example, sodium lauryl sulphate, ammonium lauryl sulfate, sodium lauryl tri(oxyethyl) sulfate, ammonium dodecyl ether sulfate, sarcosyl, oil base sodium succinate, dodecyl 2-Sulfosuccinic acid ammonium, dodecylbenzene sodium sulfonate, the DBSA triethanolamine is suitable.
Suitable amphoteric surfactant for example is an alkyl betaine, the alkylamidoalkyl CAB, the alkyl sulfobetaines, the alkyl glycinate, the alkyl carboxyl glycinate, both sexes acetate alkyl salt (Alkylamphoacetate) or both sexes alkyl propionate (Alkylamphopropionate), both sexes alkyl diacetin (Alkylamphodiacetate) or both sexes alkyl dipropionate (Alkylamphodipropionate).
For example can use the coco dimethyl sulfopropyl betaine, empgen BB, cocamidopropyl betaine or N-cocamidopropyl ethyl-N-hydroxyethyl alanine sodium.
Suitable non-ionic surface active agent for example is the product that has aliphatic alcohol or alkyl phenol and the ethylene oxide and/or the propylene oxide of 6-20 carbon atom in the alkyl chain linear or branching being.The amount of oxyalkylene is about 6-60 moles/mole alcohol.Also suitable is alkyl amine oxide, single-or dialkyl group alkanolamide, the fatty acid ester of Polyethylene Glycol, ethoxylated fatty acid amide, alkyl polyglycoside or sorbitan ether-ether.
In addition, washing, shower and bath can comprise cationic surfactant commonly used with preparation, for example quaternary ammonium compound, for example hexadecyltrimethylammonium chloride.
In addition, also can use other cationic polymer commonly used, the copolymer of acrylamide and dimethyl diallyl ammonium chloride (Polyquaternium-7) for example, cationic cellulose derivative (Polyquaternium-4,-10), Rhaball Gum CG-M 8M (INCI: the hydroxypropyl Rhaball Gum CG-M 8M), copolymer (the Polyquaternium-16 of N-vinyl pyrrolidone and quaternary ammonium N-vinyl imidazole,-44,-46), with the copolymer (Polyquaternium-11) of dithyl sulfate quaternised N-vinyl pyrrolidone/dimethylaminoethyl acrylate methyl base amino-ethyl ester etc.
In addition, washing and shower gels preparaton and bath can also comprise thickening agent with preparation, sodium chloride for example, Polyethylene Glycol-55, oleic acid propylene glycol ester, polyoxyethylene (120) methyl Fructus Vitis viniferae ether dioleate etc., and antiseptic, other active component, auxiliary agent and water.
The hair cosmetic preparation especially is included in setting agent and/or the conditioner in the hair cosmetic preparation, as hair inorganic agent, hair mousse, (hair) gel or hair spray, hair caring breast, hair conditioner, shampoo, the hair emulsion is made a start and is used fluid, long-acting setting lotion nertralizer, hair coloring agent and bleach, " hot oil processing " preparation, conditioner, hair style fixative or hair spray.Depend on application, the hair cosmetic preparation can be with (aerosol) spray, (aerosol) foam, and gel, gel spray, unguentum, the form of emulsion or wax is used.
In preferred embodiments, hair cosmetic preparaton of the present invention comprises
A) polymer of the present invention of 0.05-20 weight %,
B) water of 20-99.95 weight % and/or alcohol,
C) other composition of 0-79.5 weight %.
" alcohol " is interpreted as referring to all alcohol commonly used in cosmetics, ethanol for example, isopropyl alcohol, normal propyl alcohol.
" other composition " is interpreted as referring to additive commonly used in cosmetics, propellant for example, and antifoaming agent, interfacial activity chemical compound (being surfactant), emulsifying agent, foam forms agent and solubilizer.Employed interfacial activity chemical compound can be an anion, cation, both sexes or neutral.Other composition commonly used can for example be an antiseptic also, aromatic oil, opacifier, active component, ultraviolet filtering agent, care substance, as pantothenylol, collagen, vitamin, protein hydrolysate, α-and beta-hydroxycarboxylic acids, stabilizing agent, pH regulator agent, dyestuff, viscosity modifier, gel former, salt, wetting agent, fatting agent, compounding ingredient and other typical additives again.
Operable gel former is all gel formers commonly used in the cosmetics.They comprise slight crosslinked polyacrylic acid, such as Carbomer (INCI) or acrylate/acrylic acid C10-30 alkyl ester cross-linked polymer (INCI), acrylate/Beheneth-25 (polyoxyethylene (25) behenyl alcohol ether) methacrylate copolymer (INCI), the PVM/MA decadiene crosslinked polymer, cellulose derivative such as hydroxypropyl cellulose, hydroxyethyl-cellulose, cation-modified cellulose, polysaccharide such as HANSHENGJIAO, the hydroxypropyl starch phosphate ester, the potato starch of modification, the caprylic/capric triglyceride, sodium acrylate copolymer, Polyquaternium-32 (with) paraffin oil (Paraffinum Liquidum) (INCI), sodium acrylate copolymer (with) paraffin oil (with) PPG-1 Trideceth-6, acrylamido oxypropyl trimethyl ammonium chloride/acrylamide copolymer, steareth-10 (stearyl polyoxyethylene (10) ether) allyl ether acrylate copolymer, Polyquaternium-37 (with) paraffin oil (with) PPG-1 Trideceth-6, polyacrylamide and C13-14 isoparaffin and lauryl gather polyoxyethylene (7) ether, C13-14 isoparaffin and mineral oil and sodium polyacrylate and polyacrylamide and Polysorbate 85 (anhydrosorbitol polyoxyethylene (20) ether trioleate), C13-14 isoparaffin and isostearic acid iso stearyl ester and sodium polyacrylate and polyacrylamide and Polysorbate 60 (anhydrosorbitol polyoxyethylene (20) ether stearate), acrylate/amino acrylates/C10-30 alkyl PEG-20 itaconate copolymeric, acrylate/steareth-20 (stearyl polyoxyethylene (20) ether) itaconate copolymeric, acrylate/ceteth-20 (cetyl polyoxyethylene (20) ether) itaconate copolymeric, Polyquaternium-37 (with) propylene glycol dicaprylate dicaprate (with) PPG-1 Trideceth-6, Polyquaternium-7, Polyquaternium-44.
Set very specific performance properties if desired, also comprise herein be in the cosmetics known can with polymer coupling of the present invention all the typing and conditioner polymer.
Suitable conventional hair cosmetic polymer for example is an anionic polymer.This type of anionic polymer is the homopolymer and the copolymer of acrylic acid and methacrylic acid or its salt, the copolymer of acrylic acid and acrylamide and salt thereof; Multi-hydroxy carboxy acid's sodium salt, water solublity or water-dispersible polyester, polyurethane (Luviset P.U.R.) and polyureas.Specially suitable polymer is the copolymer (Luvimer for example of tert-butyl acrylate, acrylic acid ethyl ester, methacrylic acid 100P), N tert butyl acrylamide, acrylic acid ethyl ester, acrylic acid copolymer (Ultrahold 8, strong), vinyl acetate .beta.-methylacrylic acid and suitable, the copolymer of other vinyl esters (Luviset for example Each grade), copolymer-maleic anhydride (optional with alcohol reaction), anion polysiloxane (for example carboxy-functionalized those), the copolymer of vinyl pyrrolidone, tert-butyl acrylate, methacrylic acid (Luviskol for example VBM).
In addition, be fit to for example comprise Balance with the polymer of polymer coupling of the present invention CR (National Starch; Acrylate copolymer), Balance 0/55 (National Starch; Acrylate copolymer), Balance 47 (National Starch; Octyl acrylamide/acrylate/metering system acid butyl amino-ethyl ester copolymer), Aquaflex FX 64 (ISP; Isobutene ./ethyl maleimide/ethoxy maleimide copolymer), Aquaflex SF-40 (ISP/NationalStarch; VP/ caprolactam/DMAPA acrylate copolymer), Allianz LT-120 (ISP/Rohm ﹠amp; Haas; Acrylate/C 1-2Succinate/hydroxy acrylate copolymer), Aquarez HS (Eastman; Polyester-1), Diaformer Z-400 (Clariant; Methacryl ethyl betanin/methacrylate copolymer), Diaformer Z-711 (Clariant; Methacryl ethyl n-oxide/methacrylate copolymer), Diaformer Z-712 (Clariant; Methacryl ethyl n-oxide/methacrylate copolymer), Omnirez 2000 (ISP; Single ethyl ester of poly-(methyl vinyl ether/maleic acid) in ethanol), Amphomer HC (National Starch; Acrylate/octyl acrylamide copolymer), Amphomer 28-4910 (National Starch; Octyl acrylamide/acrylate/metering system acid butyl amino-ethyl ester copolymer), Advantage HC 37 (ISP; The terpolymer of caprolactam/vinyl pyrrolidone/dimethylaminoethyl acrylate methyl base amino-ethyl ester), Acudyne 258 (Rohm ﹠amp; Haas; Acrylate/hydroxy ester acrylate copolymer), Luviset PUR (BASF, polyurethane-1), Luviflex Silk (BASF), Eastman AQ48 (Eastman).
Anionic polymer very particularly preferably is an acid number more than or equal to the copolymer of 120 polyacrylate and tert-butyl acrylate, acrylic acid ethyl ester, methacrylic acid.
Other suitable hair cosmetic polymer is the cationic polymer with INCI title Polyquaternium, for example copolymer (the Luviquat of vinyl pyrrolidone/N-vinyl imidazole salt FC, Luviquat HM, Luviquat MS, Luviquat Care), use the copolymer (Luviquat of the quaternised N-vinyl pyrrolidone of dithyl sulfate/dimethylaminoethyl acrylate methyl base amino-ethyl ester PQ 11), the copolymer (Luviquat of N-caprolactam/N-vinyl pyrrolidone/N-vinyl imidazole salt Hold); Cationic cellulose derivative (Polyquaternium-4 and-10), acrylamide copolymer (Polyquaternium-7).
In addition, also can use cationic guar derivative such as Rhaball Gum CG-M 8M (INCI).
Other suitable hair cosmetic polymer also has neutral polymer, as the polyvinyl pyrrolidone class, the copolymer of N-vinyl pyrrolidone and vinyl acetate and/or propionate, polysiloxanes, Vinylcaprolactam homopolymer and contain the N-vinylpyrrolidone copolymers, polymine and salt thereof, polyvinylamine and salt thereof, cellulose derivative, polyaspartic acid salts and derivant.
In order to produce some performance, preparation can additionally comprise the conditioning material based on polysiloxane compound.Suitable polysiloxane compound for example is poly-alkylsiloxane, poly-aryl siloxanes, poly-aryl alkyl siloxanes, polyether silicone, organic siliconresin or dimethicone copolyol (CTFA) and amino functionalised chemical compound such as amino-terminated polydimethylsiloxane (CTFA).
Polymer of the present invention is particularly suitable at the hair styling preparation, especially is used as setting agent in hair spray (aerosol type spray and do not have the pump power spray of propellant gas) and the hair mousse (aerosol mouse and do not have the pump power mousse of propellant gas).
Embodiment
Polymer prepares in water by radical polymerization commonly used.Below describe the synthetic of polymer I, II, III, IV, they can be the representatives of all other preparation sections.
I: the copolymer of polymeric monomer A, B, C in the presence of polymer E
At 5 weight % (based on monomeric total amount) Mowiol There is the polymer of preparation 56.5 weight %N-vinyl pyrrolidones, 40 weight % caprolactams and 3.5 weight % vinyl imidazoles down in 4-88
At first introduce 10 gram Mowiol The solution of 4-88 in 50 gram water, and be heated to 75 ℃.In 3 hours, add 113 gram vinyl pyrrolidones, 7 gram vinyl imidazoles and the solution of 80 gram caprolactams in 300 gram water then, adding the monomeric while, begin to add the solution of 1 gram Wako V 50 in 100 gram water, the reinforced time is 4 hours.Then, under 75 ℃ internal temperature with mixture post polymerization 2 hours.
II: the copolymer of monomer A, B, C, D
Prepare 55.0 weight %N-vinyl pyrrolidones, 40 weight % caprolactams, 2.5 weight % vinyl imidazoles and 2.5 weight %Bisomer The polymer of S10W (Laport)
At first introduce 200 gram water, and be heated to 75 ℃.In 2 hours, add 110 gram vinyl pyrrolidones, 5 gram vinyl imidazoles, 5 gram Bisomer then S10W and the solution of 80 gram caprolactams in 195 gram water are adding the monomeric while, begin to add the solution of 1 gram Wako V 50 in 20 gram water, and the reinforced time is 2.5 hours.Then, under 75 ℃ internal temperature with mixture post polymerization 1 hour.
III: the copolymer of polymeric monomer A, B, C, D in the presence of polymer E
At 5 weight % (based on monomeric total amount) Pluriol There is the polymer of preparation 55 weight %N-vinyl pyrrolidones, 35 weight % caprolactams, 2 weight % vinyl imidazoles and 8% vinyl formamide down in E 4000
At first with 10 gram Pluriol E 4000 is incorporated in the 200 gram water, and is heated to 75 ℃.In 2 hours, add 110 gram vinyl pyrrolidones, 4 gram vinyl imidazoles, 16 gram vinyl formamides and the solution of 70 gram caprolactams in 195 gram water then, adding the monomeric while, begin to add the solution of 1 gram Wako V 50 in 20 gram water, the reinforced time is 2.5 hours.Then, under 75 ℃ internal temperature with mixture post polymerization 1 hour.
IV: the copolymer of monomer A, B, C
The polymer for preparing 51.5 weight %N-vinyl pyrrolidones, 45 weight % caprolactams and 3.5 weight % vinyl imidazoles
At first introduce 50 gram water, and be heated to 75 ℃.In 3 hours, add 103 gram vinyl pyrrolidones, 7 gram vinyl imidazoles and the solution of 90 gram caprolactams in 300 gram water then, adding the monomeric while, begin to add the solution of 1 gram Wako V 50 in 100 gram water, the reinforced time is 4 hours.Then, under 75 ℃ internal temperature with mixture post polymerization 2 hours.
Estimate gel formulation according to following standard:
Outward appearance:
Estimate the transparency of each gel with respect to known standard:
1 is transparent suitable with Luviskol K 30
2 is almost transparent suitable with Luviskol K 90
3 is muddy a little poorer than Luviskol K 90
4 muddinesses
5 emulsus
Viscosity:
According to Kempf 75% with 90% relative atmospheric humidity and room temperature under directly measure viscosity on the dry film at gel formulation.
1 is not sticking
2 is a little a bit sticking
3 moderate tack
4 is very sticking
Bending rigidity:
On hair locks, measure bending rigidity with Gel Treatment.
1??＞180cN
2??＞150cN
3??＞120cN
4??＞90cN
5??＞60cN
Hair style persistency after the solution-treated:
On the hair locks of handling with 3% aqueous polymers solution (aqueous solution), measure the hair style persistency.
1??＞50％????2??＞40％
3??＞30％????4??＞20％
Hair style persistency after the Gel Treatment:
Using mensuration hair style persistency on the hair locks of Gel Treatment.
1??＞80％????2??＞70％
3??＞60％????4??＞50％
Comparative Examples:
Form Outward appearance 25 ℃ of viscosity (Kempf), 75% relative humidity 25 ℃ of viscosity (Kempf), 90% relative humidity Bending rigidity [cN] CR[%] solution, 3% aqueous solution, 25 ℃, 90% relative humidity CR[%] gel, 25 ℃, 90% relative humidity
??LuvitecVPC ??3 ????- ????- ????- ????- ????-
??Luviskol?Plus ??4 ????- ????- ????- ????- ????-
??Luviskol?K?30 ??1 ????2 ????3 ????5 ????4 ????4
??Luvsikol?K?90 ??2 ????3 ????3 ????2 ????4 ????3
??Luviskol?VA?64 ??2 ????1 ????5 ????5 ????4 ????4
1: 1 copolymer of Luvitec VPC:VP/VCap
The homopolymer of Luviskol Plus:VCap
The homopolymer of Luviskol K 30:VP
The homopolymer of Luvsikol K 90:VP
3: 2 copolymers of Luviskol VA 64:VP/Vac
Embodiment 1:
The VP-VCap-VI copolymer systems
Form Ratio Outward appearance Viscosity (Kempf), 25 ℃, 75% relative humidity Viscosity (Kempf), 25 ℃, 90% relative humidity Bending rigidity [N] CR[%] solution, 3% aqueous solution, 25 ℃, 90% relative humidity CR[%], 25 ℃, 90% relative humidity
??a) ????VP/VI/VCap ????60/10/30 ????4-5 ????- ????- ????- ????- ????-
??b) ????VP/VI/VCap ????37/3/60 ????4-5 ????- ????- ????- ????- ????-
??c) ????VP/VCap ????60/40 ????1 ????1 ????1-2 ????4 ????3 ????1
??d) ????VP/VI/VCap ????65/5/30 ????4 ????0 ????2 ????1 ????2 ????1
??e) ????VP/VI/VCap ????50/5/45 ????4 ????0 ????1-2 ????1 ????2 ????1
??f) ??VP/VI/VCap ????56.5/3.5/40 ???2 ????1 ????3 ????1 ????3 ????1
??g) ??VP/VI/VCap ????57/3/40 ???1 ????1 ????2 ????1 ????3 ????1
??h) ??VP/VI/VCap ????57.5/2.5/40 ???1 ????1 ????2 ????1 ????3 ????1
??i) ??VP/VI/VCap ????62.5/2.5/35 ???1 ????1 ????1-2 ????4 ????2
??j) ??VP/VI/VCap ????58.5/1.5/40 ???1 ????1 ????1-2 ????2 ????3 ????1
??k) ??VP/VI/VCap ????52.5/2.5/45 ???1 ????1 ????1-2 ????1 ????3 ????1
??l) ??VP/VI/VCap ????53/2/45 ???1 ????1 ????1-2 ????1 ????3 ????1
??m) ??VP/VI/VCap ????51.5/3.5/45 ???2-3 ????1 ????2 ????1 ????3 ????1
Embodiment 2:
Comprise other monomer D (embodiment 2d) or polymerization in the presence of polymer E (embodiment 2a)+2b)) or comprise the VP-VCap-VI copolymer systems of other monomer D and polymerization in the presence of polymer E (embodiment 2c)
Form Ratio Outward appearance 25 ℃ of viscosity (Kempf), 75% relative humidity 25 ℃ of viscosity (Kempf), 90% relative humidity Bending rigidity [cN] CR[%] solution 3% aqueous solution, 25 ℃ of 90% relative humidity CR[%] 25 ℃, 90% relative humidity
??a) ????VP/VI/VCap+ ????Mowiol?4-88 56.5/3.5/40 5 weight % ??1-2 ????1 ????1-2 ????1 ????3
??b) ????VP/VI/VCap+ ????Tylose?H?4000?G 60/2.5/37.5 5 weight % ??1 ????1 ????2 ????1 ????3
??c) ????VP/VI/VCap/VFA+ ????Pluriol?E?4000 55/,2/3,5/8 5 weight % ??1-2 ????1-2 ????3 ????2 ????3
??d) ????VP/VI/VCap/ ????Bisomer?S10W ??55/2.5/40/2.5 ??1 ????2 ????4 ????1 ????3
Use
Preparation section:
Carbopol gel (200 gram)
Be in 3% polymer among the 0.5%Carbopol (940 or Ultrez 21)
Batch of material is a):
98.68 gram Carbopol stock solution (with 1% intensity of Euxyl K 100 preservations)
1.32 the gram triethanolamine is in 250 ml beakers
Use agitator (about 90rpm) that TEA is incorporated in the stock solution, till mixture is transparent (about 15 minutes)
Batch of material b):
6.00 gram polymer (solid)
Add to and reach the required distilled water of 100 grams, in 250 milliliters of Erlenmeyer
If dissolving fully batch of material b), then under identical agitator speed, use Dropping funnel with it be incorporated at leisure batch of material a) in (about 1 droplet/second).If after dripping solution, form final gel, then it carried out the back stir about 30 minutes again.
Shampoo
Preparation:
All components is dissolved in the water, regulates pH value, add thickening agent then.
The aerosol type spray
Preparation:
Be weighed into all components.Regulate pH value, and clear solution packed into contain in the pressurized container of gas propellant.
Wax
Preparation:
Be weighed into this each component in mutually, fusion also stirs.
Aerosol mousse
Preparation:
Mix fragrant oil phase.Each component and the mixing that add the water-ethanol phase in succession.If mention, add thickening agent and stirring till uniform distribution.Regulate pH value.Pack into and contain in the pressurized container of propellant gas.
Pump type hair spray
Preparation:
Stir water.Add each component and the uniform distribution of ethanol in mutually in succession.Then all components is encased in the pump type hair spray bottle.
Pump type mousse
Preparation:
Prepare the homogeneous mixture of each component and the pump type mousse bottle of packing in.
O/W type emulsion (hair conditioner etc.)
Preparation:
With oil phase and emulsifier (at high temperature in case of necessity), and add water (with possible thickening agent, at high temperature in case of necessity), stir and homogenize.
Prescription:
Comprise embodiment 1g)-polymer in 1l) and the hair gel of Luviskol K30
% material supplier INCI
0.50??Carbopol?940????????(6)????????Carbomer
87.60 remove the fossil water demineralized water
0.70 triethanolamine Care (1) triethanolamine
Polymer 1g)-1l) 6.00 (1)
5.00 Luviskol K30 solution (1) PVP
An amount of aromatic oil
The addition of C remophor RH 40 (1) PEG-40 castor oil hydrogenated
0.10 Euxyl K100 (42) benzylalcohol, methyl chloride is for isothiazolone,
Methylisothiazolinone
0.10 vitamin e acetate vitamin e acetate
Supplier
(1)???BASF?Aktiengesellschaft
(6)???B.F.Goodrich?Company?Chemical?Division
(42)??Schülke?&?Mayr?GmbH
Comprise embodiment 1g)-polymer in 1l) and the hair gel of Luviskol VA64
% material supplier INCI
0.50??Carbopol?980????????(6)?????????Carbomer
87.60 remove the fossil water demineralized water
0.90 Neutrol TE (1) tetrahydroxypropyl ethylenediamine
Polymer 1g)-1l) 7.00 (1)
4.00 Luviskol VA64 W (1) VP/VA copolymer
An amount of aromatic oil
The addition of C remophor CO 40 (1) PEG-40 castor oil hydrogenated
0.10 Euxyl K100 (42) benzylalcohol, methyl chloride is for isothiazolone,
Methylisothiazolinone
0.10 1,2-propylene glycol Care (1) propylene glycol
Supplier
(1)???BASF?Aktiengesellschaft
(6)???B.F.Goodrich?Company?Chemical?Division
(42)??Schülke?&?Mayr?GmbH
Comprise embodiment 1g)-polymer in 1l) and the hair gel of Luviskol K90
% material supplier INCI
0.50??Carbopol?ETD?2001????(6)?????Carbomer
87.60 demineralized water demineralized water
0.70 triethanolamine Care (1) triethanolamine
Polymer 1g)-1l) 6.00 (1)
5.00??Luviskol?K90?????????(1)?????PVP
An amount of aromatic oil
The addition of C remophor CO 40 (1) PEG-40 castor oil hydrogenated
0.10 Nipagin M (34) methyl parahydroxybenzoate
0.10 isopropyl myristate (27) isopropyl myristate
Supplier
(1)???BASF?Aktiengesellschaft
(6)???B.F.Goodrich?Company?Chemical?Division
(34)??Nipa?Laboratories?Ltd.
(27)??Cognis?Deutschland?GmbH
Comprise embodiment 1g)-polymer in 1l) and the hair gel of Luviquat Hold
% material supplier INCI
Polymer 1g)-1l) 10.00 (1)
2.50??Luviquat?Hold??????(1)????????Polyquaternium-46
15.00 ethanol 96% ethanol
70.30 remove the fossil water demineralized water
5.00??Luviskol?K90???????(1)????????PVP
0.10 aromatic oil
0.10 glycerol (20) glycerol
2.00 Natrosol 250 HR (4) hydroxyethyl-cellulose
Supplier
(1)???BASF?Aktiengesellschaft
(6)???B.F.Goodrich?Company?Chemical?Division
(20)??Merck?KGaA
(4)???Aqualon?GmbH
Comprise embodiment 1g)-polymer in 1l) and the hair gel of Amaze
% material supplier INCI
Polymer 1g)-1l) 6.00 (1)
2.00 the corn starch of Amaze (72) modification
0.50 Hydagen HCMF (27) chitosan
An amount of aromatic oil
The addition of C remophor CO 40 (1) PEG-40 castor oil hydrogenated
0.10 Abil 8843 (44) PEG-14 polydimethylsiloxane
0.10 Euxyl K100 (42) benzylalcohol, methyl chloride is for isothiazolone, first
The base isothiazolone
91.40 remove the fossil water demineralized water
Supplier
(1)???BASF?Aktiengesellschaft
(6)???B.F.Goodrich?Company?Chemical?Division
(27)??Cognis?Deutschland?GmbH
(42)??Schülke?&?Mayr?GmbH
(44)??Th.Goldschmidt?AG
(72)??National?Starch?&?Chemical?Limited
Comprise embodiment 1g)-polymer in 1l) and the hair gel of Styleze CC-10
% material supplier INCI
Polymer 1g)-1l) 8.00 (1)
5.00 Styleze CC-10 (65) VP/DMAPA acrylate copolymer
0.05 AMP (56) amino methyl propanol
84.85 remove the fossil water demineralized water
An amount of aromatic oil
The addition of C remophor RH 40 (1) PEG-40 castor oil hydrogenated
0.10 Dow Corning 190 (16) dimethicone copolyols
0.10??Euxyl?K100??????????(42)
2.00 Klucel (4) hydroxypropyl cellulose
Supplier
(1)???BASF?Aktiengesellschaft
(4)???Aqualon?GmbH
(16)??Dow?Corning?Corporation
(42)??Schülke?&?Mayr?GmbH
(56)??Angus?Chemical?Company
(65)??ISP?Global?Technologies?Deutschland?GmbH
Comprise embodiment 1g)-polymer in 1l) and the hair gel of Styleze 2000
% material supplier INCI
Polymer 1g)-1l) 6.00 (1)
1.00 Styleze 2000 (65) VP/ acrylate/methacrylic acid lauryls
Ester copolymer
0.26 AMP (56) amino methyl propanol
90.64 remove the fossil water demineralized water
An amount of aromatic oil
The addition of C remophor RH 40 (1) PEG-40 castor oil hydrogenated
0.10 Karion F liquid (20) Sorbitol
0.10 Euxyl K100 (42) benzylalcohol, methyl chloride is for isothiazolone, first
The base isothiazolone
2.00 hydroxypropyl guar gum-hydroxypropyl guar gum
Supplier
(1)???BASF?Aktiengesellschaft
(20)??Merck?KGaA
(42)??Schülke?&?Mayr?GmbH
(56)??Angus?Chemical?Company
(65)??ISP?Global?Technologies?Deutschland?GmbH
Comprise embodiment 1g)-polymer in 1l) and the hair gel of Allianz LT-120
% material supplier INCI
0.50??Ultrez?10???????????(6)???????Carbomer
90.01 remove the fossil water demineralized water
0.70 triethanolamine Care (1) triethanolamine
Polymer 1g)-1l) 6.00 (1)
2.00 Allianz LT-120 (61) acrylate/C1-2 succinate/hydroxyl-third
The olefin(e) acid ester copolymer
0.19 AMP (56) amino methyl propanol
An amount of aromatic oil
The addition of C remophor CO 40 (1) PEG-40 castor oil hydrogenated
0.10 Pluracare E400 (1) PEG-8 (Polyethylene Glycol-8)
0.10??Euxyl?K100??????????(42)
0.50 Natrosol 250 HR (4) hydroxyethyl-cellulose
Supplier
(1)???BASF?Aktiengesellschaft
(4)???Aqualon?GmbH
(6)???B.F.Goodrich?Company?Chemical?Division
(42)??Schülke?&?Mayr?GmbH
(56)??Angus?Chemical?Company
(61)??Rhm?&?Haas?GmbH
Comprise embodiment 1g)-polymer in 1l) and the hair gel of Fixomer A30
% material supplier INCI
Polymer 1g)-1l) 7.00 (1)
7.00??Fixomer?A30?????????????-
0.70 triethanolamine Care (1) triethanolamine
An amount of aromatic oil
The addition of C remophor CO 40 (1) PEG-40 castor oil hydrogenated
0.10 D-Panthenol USP (1) pantothenylol
0.10 Euxyl K100 (42) benzylalcohol, methyl chloride is for isothiazolone, first
The base isothiazolone
84.90 remove the fossil water demineralized water
1.00??Sepigel?305?????????????(175)
Supplier
(1)???BASF?Aktiengesellschaft
(42)??Schülke?&?Mayr?GmbH
(175)?Seppic
Comprise embodiment 1g)-polymer in 1l) and the hair gel of PVF
% material supplier INCI
0.50??Carbopol?940????????????(6)?????????Carbomer
90.50 remove the fossil water demineralized water
0.70 triethanolamine Care (1) triethanolamine
Polymer 1g)-1l) 7.00 (1)
1.00 PVF (72) polyvinyl formamide
An amount of aromatic oil
The addition of C remophor RH 40 (1) PEG-40 castor oil hydrogenated
0.10 Euxyl K100 (42) benzylalcohol, methyl chloride is for isothiazolone, first
The base isothiazolone
0.10 Uvinul MC 80 (1) methoxy cinnamic acid ethyl hexyl ester
0.10 Abil 8843 (44) PEG-14 polydimethylsiloxane
Supplier
(1)??BASF?Aktiengesellschaft
(6)??B.F.Goodrich?Company?Chemical?Division
(42)?Schülke?&?Mayr?GmbH
(44)?Th.Goldschmidt?AG
(72)?National?Starch?&?Chemical?Limited
Comprise embodiment 1g)-hair gel of polymer in 1l)
% material supplier INCI
0.50?Carbopol?940????????(6)???????Carbomer
88.50 remove the fossil water demineralized water
0.70 triethanolamine Care (1) triethanolamine
Ethylenediamine
Polymer 1g)-1l) 10.00 (1)
An amount of aromatic oil
The addition of C remophor CO 40 (1) PEG-40 castor oil hydrogenated
0.10 Euxyl K100 (42) benzylalcohol, methyl chloride is for isothiazolone, first
The base isothiazolone
0.10 1,2-propylene glycol Care (1) propylene glycol
0.10 isopropyl myristate (27) isopropyl myristate
Supplier
(1)??BASF?Aktiengesellschaft
(6)??B.F.Goodrich?Company?Chemical?Division
(27)??Cognis?Deutschland?GmbH
(42)??Schülke?&?Mayr?GmbH
Comprise embodiment 1g)-hair gel of polymer in 1l)
% material supplier INCI
Polymer 1g)-1l) 10.00 (1)
15.00 96% ethanol
72.70 remove the fossil water demineralized water
0.10 aromatic oil
0.10 glycerol (20) glycerol
0.10 D-panthenol USP (1) pantothenylol
2.00 Natrosol 250 HR (4) hydroxyethyl-cellulose
Supplier
(1)???BASF?Aktiengesellschaft
(6)???B.F.Goodrich?Company?Chemical?Division
(20)??Merck?KGaA
(4)???Aqualon?GmbH
Comprise embodiment 1g)-hair gel of polymer in 1l)
% material supplier INCI
0.50??Carbopol?ETD?2001???(6)???????Carbomer
88.50 remove the fossil water demineralized water
0.70 triethanolamine Care (1) triethanolamine
Polymer 1g)-1l) 10.00 (1)
An amount of aromatic oil
The addition of C remophor CO 40 (1) PEG-40 castor oil hydrogenated
0.10 Nipagin M (34) methyl parahydroxybenzoate
0.10 Uvinul MC 80 (1) methoxy cinnamic acid ethyl hexyl ester
0.10 Abil 8843 (44) PEG-14 polydimethylsiloxane
Supplier
(1)???BASF?Aktiengesellschaft
(6)???B.F.Goodrich?Company?Chemical?Division
(34)??Nipa?Laboratories?Ltd.
(44)??Th.Goldschmidt?AG
Comprise embodiment 1g)-hair gel of polymer in 1l)
% material supplier INCI
Polymer 1g)-1l) 10.00 (1)
An amount of aromatic oil
The addition of C remophor CO 40 (1) PEG-40 castor oil hydrogenated
0.10 Palatinol A (1) diethyl phthalate
0.10 Luvitol EHO (1) thylhexoic acid 16/octadecane ester
0.10 Cetiol HE (27) polyoxyethylene (7) glycerin ether cocos nucifera oil acid esters
0.10 Euxyl K100 (42) benzylalcohol, methyl chloride is for isothiazolone, first
The base isothiazolone
87.70 remove the fossil water demineralized water
2.00 Luvigel EM (1) caprylic/capric triglyceride, acrylate
Copolymer
Supplier
(1)???BASF?Aktiengesellschaft
(27)??Cognis?Deutschland?GmbH
(42)??Schülke?&?Mayr?GmbH
Comprise embodiment 1g)-the typing solution of polymer in 1l)
% material supplier INCI
62.60 96% ethanol ethanol
30.00 remove the fossil water demineralized water
0.10 Dow Corning 190 polyethers (16) dimethicone copolyol
0.10 aromatic oil
0.10 Uvinul MC 80 (1) methoxy cinnamic acid ethyl hexyl ester
0.10 D-panthenol USP (1) pantothenylol
Polymer 1g)-1l) 7.00 (1)
Supplier
(1)???BASF?Aktiengesellschaft
(16)??Dow?Corning?Corporation
Comprise embodiment 1g)-the typing solution of polymer in 1l)
% material supplier INCI
0.10 Dow Corning 190 polyethers (16) dimethicone copolyol
0.05 Dow Corning 344 liquid (16) cyclomethicone
An amount of aromatic oil
53.85 96% ethanol ethanol
40.00 remove the fossil water demineralized water
Polymer 1g)-1l) 6.00 (1)
Supplier
(1)???BASF?Aktiengesellschaft
(16)??Dow?Corning?Corporation
Comprise embodiment 1g)-the typing solution of polymer in 1l)
% material supplier INCI
0.10 D-panthenol USP (1) pantothenylol
0.10??Nutrilan?Keratin?W
0.10 Elastin PG 2000 elastin hydrolysis
0.40 Uvinul M 40 (1) Benzophenone-3 (2-hydroxyl-4-methoxy
The base benzophenone)
10.00 remove the fossil water demineralized water
84.30 96% ethanol ethanol
An amount of aromatic oil
Polymer 1g)-1l) 5.00 (1)
Supplier
(1)???BASF?Aktiengesellschaft
Comprise embodiment 1g)-polymer in 1l) and the typing solution of Luviquat FC 550
% material supplier INCI
4.00 (1) Vinylcaprolactam homopolymer polymer 1g)-1l)
3.50??Luviquat?FC?550???(1)????Polyquaternium-16
72.20 96% ethanol ethanol
20.00 remove the fossil water demineralized water
An amount of aromatic oil
Supplier
(1)???BASF?Aktiengesellschaft
Comprise embodiment 1g)-the typing solution of polymer in 1l)
% material supplier INCI
Polymer 1g)-1l) 4.00 (1)
0.20??Pluracare?E?400???(1)??????PEG-8
0.10 aromatic oil
10.00 remove fossil water
85.70 96% ethanol ethanol
Supplier
(1)???BASF?Aktiengesellschaft
Comprise embodiment 1g)-the pump type hair spray of polymer in 1l)
% material supplier INCI
Polymer 1g)-1l) 26.00 (1)
73.70 96% ethanol ethanol
0.10 aromatic oil
0.10 Uvinul MC 80 (1) methoxy cinnamic acid ethyl hexyl ester
0.10 Dow Corning 190 (16) PEG/PPG-18/18 polydimethylsiloxane
Supplier
(1)???BASF?Aktiengesellschaft
(16)??Dow?Corning?Corporation
Comprise embodiment 1g)-the pump type hair spray of polymer in 1l)
% material supplier INCI
Polymer 1g)-1l) 26.00 (1)
4.00 Luviskol Plus (1) Vinylcaprolactam homopolymer
69.60 96% ethanol ethanol
0.10 Uvinul MC 80 (1) methoxy cinnamic acid ethyl hexyl ester
0.10 Dow Corning 344 (16) cyclomethicones
0.10 Dow Corning 556 (16) Silicone DC 556s
Supplier
(1)???BASF?Aktiengesellschaft
(16)??Dow?Corning?Corporation
Comprise embodiment 1g)-the aerosol type spray NON VOC of polymer in 1l)
% material supplier INCI
Polymer 1g)-1l) 13.00 (1)
0.10 aromatic oil
0.10 1,2-propylene glycol Care (1) propylene glycol
0.10 Citroflex 2 (53) triethyl citrates
46.70 remove the fossil water demineralized water
40.00 HFC 152A-hydrogen fluorohydrocarbon 152a
Supplier
(1)???BASF?Aktiengesellschaft
(53)??Pfizer?Chemie
Comprise embodiment 1g)-polymer in 1l) and the aerosol type spray NON VOC of Luviset CAN
% material supplier INCI
Polymer 1g)-1l) 10.00 (1)
2.00 Luviset CAN (1) VA/ crotonates/vinyl neodecanoate copolymerization
Thing
0.16 AMP (56) amino methyl propanol
0.10 aromatic oil
0.10 phytantriol (1) phytantriol
52.64 demineralized water demineralized water
35.00 HFC 152A-hydrogen fluorohydrocarbon 152a
Supplier
(1)???BASF?Aktiengesellschaft
(56)??Angus?Chemical?Company
Comprise embodiment 1g)-polymer in 1l) and the aerosol type spray VOC 55 of Luviset P.U.R.
% material supplier INCI
Polymer 1g)-1l) 7.00 (1)
7.00 Luviset P.U.R. (1) polyurethane-1 neodecanoic acid ester copolymer
14.30 dehydrated alcohol ethanol
36.50 remove the fossil water demineralized water
0.10 1,2-propylene glycol Care (1) propylene glycol
0.10 aromatic oil
40.00 DME-dimethyl ether
Supplier
(1)???BASF?Aktiengesellschaft
Comprise embodiment 1g)-polymer in 1l) and the aerosol type spray VOC 55 of Luviskol Plus
% material supplier INCI
Polymer 1g)-1l) 10.00 (1)
5.00 Luviskol Plus. (1) Vinylcaprolactam homopolymer
17.00 dehydrated alcohol ethanol
32.80 remove the fossil water demineralized water
0.10 nicotiamide-nicotiamide
0.10 aromatic oil
35.00 DME-dimethyl ether
Supplier
(1)???BASF?Aktiengesellschaft
Comprise embodiment 1g)-polymer in 1l) and the aerosol type spray VOC 80 of Luvimer 100P
% material supplier INCI
Polymer 1g)-1l) 10.00 (1)
1.00 Luvimer 100P (1) acrylate copolymer
0.24 AMP (56) amino methyl propanol
35.00 dehydrated alcohol ethanol
8.56 demineralized water demineralized water
0.10 Belsil CM040 (156) encircles penta siloxanes
0.10 aromatic oil
10.00 normal butane-butane
35.00 DME-dimethyl ether
Supplier
(1)???BASF?Aktiengesellschaft
(56)??Angus?Chemical?Company
(156)?Wacker?Chemie?GmbH
Comprise embodiment 1g)-polymer in 1l) and the aerosol type spray VOC 80 of Luviskol VA37
% material supplier INCI
Polymer 1g)-1l) 10.00 (1)
4.00 Luviskol VA37 (1) VP/VA copolymer
38.00 dehydrated alcohol ethanol
7.70 remove the fossil water demineralized water
0.10 D-panthenol USP (1) pantothenylol
0.10 Dow Corning 556 (16) Silicone DC 556s
0.10 aromatic oil
40.00 DME-dimethyl ether
Supplier
(1)???BASF?Aktiengesellschaft
(16)??Dow?Corning?Corporation
Comprise embodiment 1g)-polymer in 1l) and Luviflex Silk but do not add the aerosol type spraying of water Agent
% material supplier INCI
Polymer 1g)-1l) 7.00 (1)
4.00 Luviflex Silk. (1) PEG/PPG-25/25 polydimethylsiloxane
/ acrylate copolymer
0.47 AMP (56) amino methyl propanol
48.23 dehydrated alcohol ethanol
0.10 Palatinol A (1) diethyl phthalate
0.10 D-panthenol USP (1) pantothenylol
0.10 aromatic oil
10.00 propane/butane-propane/butane
30.00 DME-dimethyl ether
Supplier
(1)???BASF?Aktiengesellschaft
(56)??Angus?Chemical?Company
Comprise embodiment 1g)-polymer in 1l) and Amphomer but do not add the aerosol type spray of water
% material supplier INCI
Polymer 1g)-1l) 10.00 (1)
1.00 Amphomer 28-4910 (72) acrylate copolymer
0.17 AMP (56) amino methyl propanol
43.53 dehydrated alcohol ethanol
0.10 Dow Corning 193 (16) PEG-12 polydimethylsiloxane
0.10 Dow Corning 556 (16) Silicone DC 556s
0.10 aromatic oil
45.00 DME-dimethyl ether
Supplier
(1)???BASF?Aktiengesellschaft
(16)??Dow?Corning?Corporation
(56)??Angus?Chemical?Company
(72)??National?Starch?&?Chemical?Limited
Mixed processes
Pump type mousse hair setting composition
3.00 polymer 1g)
1.00 Luviquat Mono CP ethoxy hexadecyldimethyl benzyl ammonium ammonium phosphate
0.20 Cremophor A 25 Ceteareth-25 (16/octadecanol polyoxy
Ethylene (25) ether)
0.40 aromatic oil PC 910.781/Cremophor
95.40 remove the fossil water demineralized water
An amount of antiseptic
Preparation:
Prepare the homogeneous mixture of each component and the pump type mousse bottle of packing in.
Pump type hair spray
A The addition of C remophor CO 40 PEG-40 castor oil hydrogenated
An amount of aromatic oil
75.50 remove the fossil water demineralized water
7.30 polymer 1h)
B 1.00 1,2-propylene glycol Care propylene glycol
0.20??Uvinul?P?25????????????PEG-25?PABA
1.00??Luviquat?HM?552????????Polyquaternium-16
15.00 96% ethanol ethanol
Preparation:
Stir the A phase.Each component and the uniform distribution that add the B phase in succession.Then all components is bottled.
Typing water
A 0.70 Cremophor CO 40 PEG-40 castor oil hydrogenated
0.20 aromatic oil
75.10 remove the fossil water demineralized water
7.30 polymer 1i)
B 1.00 1,2-propylene glycol Care propylene glycol
0.50??Luviquat?Care??????????Polyquaternium-44
0.20??Uvinul?P?25????????????PEG-25?PABA
15.00 96% ethanol ethanol
Preparation:
Stir the A phase.Each component and the uniform distribution that add the B phase in succession.Then all components is bottled.
Hair mousse
A 0.70 Cremophor CO 40 PEG-40 castor oil hydrogenated
0.20 aromatic oil
78.50 remove the fossil water demineralized water
B 0.50 Luviquat Mono LS methylsulfuric acid cocoyl trimethyl ammonium
6.70 polymer 1g)
2.50??Luviquat?Hold?????????Polyquaternium-46
0.20??Uvinul?P?25???????????PEG-25?PABA
0.50??Pluracare?E?400???????PEG-8
0.20??Cremophor?A?25????????Ceteareth-25
An amount of antiseptic
C 10.00 propane/butane 3.5 crust (20 ℃) propane/butane
Preparation:
Stir the A phase.Each component and the uniform distribution that add the B phase in succession.Then with C bottling together mutually.
Hair styling mousse
A 2.00 Luviquat Mono LS methylsulfuric acid cocoyl trimethyl ammoniums
An amount of aromatic oil
B 62.85 removes the fossil water demineralized water
7.00 polymer 1h)
2.00??Luviquat?PQ?11????????Polyquaternium-11
0.20??Cremophor?A?25????????Ceteareth-25
0.50 D-panthenol USP pantothenylol
0.05 Uvinul MS 40 Benzophenone-4 (5-benzoyl-4-hydroxyl
Base-2-methoxy benzenesulfonic acid)
0.20 Dow Corning 949 cationes
15.00 96% ethanol ethanol
C 0.20 Natrosol 250 HR hydroxyethyl-celluloses
D 10.00 propane/butane 3.5 crust (20 ℃) propane/butane
Preparation:
Stir the A phase.Each component and the mixing that add the B phase in succession.Adding C also stirs till uniform distribution mutually.Regulate pH to 6-7.With D bottling together mutually.
The typing foam
A 2.00 Luviquat Mono LS methylsulfuric acid cocoyl trimethyl ammoniums
An amount of aromatic oil
B 83.13 demineralized water demineralized waters
0.47 AMP amino methyl propanol
0.20 antiseptic
0.20 Abil B 8843 dimethicone copolyols
C 4.00 polymer 1l)
D 10.00 propane/butane 3.5 crust (20 ℃) propane/butane
Preparation:
Stir the A phase.With A be weighed into mutually B mutually in till transparent.With B be stirred to mutually A mutually in.
Adding C also stirs mutually.With D bottling together mutually.
Wet shape typing foam
A 3.00 Luviquat Mono LS methylsulfuric acid cocoyl trimethyl ammoniums
0.20 aromatic oil
B 78.80 removes the fossil water demineralized water
C 5.00 glycerol, 87% glycerol
An amount of antiseptic
3.00 polymer 1l)
D 10.00 propane/butane 3.5 crust (20 ℃) propane/butane
Preparation:
Stir the A phase, with B be stirred to mutually A mutually in, add the C phase, bottle together mutually with D.
The foam conditioner
5.00??Luviquat?PQ?11?????????Polyquaternium-11
5.00 polymer 1f)
0.50 Luviquat Mono CP ethoxy hexadecyldimethyl benzyl ammonium ammonium phosphate
10.00 dehydrated alcohol ethanol
0.40 aromatic oil " Carina "/Cremophor RH
An amount of antiseptic
69.10 remove the fossil water demineralized water
10.00 propane/butane propane/butane
Preparation:
Each component is claimed together, stir till uniform distribution bottling.
Bright pomade
5.00 the sad 16/octadecane ester of Luvitol EHO
5.00 Oleum Ricini Semen Ricini (Ricinus Communis) oil
17.00 vaseline vaseline
7.00 TeCero wax 103 K microwaxes
6.00 Beeswax 3044 PH Cera Flavas
Polymer 1i) 5.00 (anhydrous)
3.00 Uvinul MBC 95 4 methyl benzylidene camphors
2.00 Uvinul BMBM PAROSOL 1789
0.10 phytantriol phytantriol
0.50 phenyl phenol phenyl phenol
48.40 high viscosity paraffin oil mineral oil
.00 Dow Corning 556 liquid Silicone DC 556s
An amount of aromatic oil
Preparation:
Weigh up each component and the fusion of A phase.
Coloured face cream
A 1.50 Cremophor A 6 Ceteareth-6 (16/octodecyl alcohol polyoxyethylene (6)
Ether), stearyl alcohol
1.50??Cremophor?A?25???????????????Ceteareth-25
3.00 cetyl stearyl alcohol 16/octadecanol
6.00 the sad 16/octadecane ester of Luvitol EHO
0.30 phytantriol phytantriol
B??7.70??Luviquat?Care???????????Polyquaternium-44
6.00 polymer 1l)
2.00 1,2-propylene glycol Care propylene glycol
1.00 D-panthenol USP pantothenylol
An amount of antiseptic
70.87 remove the fossil water demineralized water
C 0.05 basic violet 14 C.I.42510, basic violet 14
0.08 red 76 C.I.12245 of alkalescence, alkalescence red 76
An amount of aromatic oil
An amount of citric acid citric acid
Preparation:
A is heated to about 80 ℃ respectively mutually with B mutually.With B evenly be stirred to mutually A mutually in, and carry out brief back homogenize.Be cooled to about 40 ℃, add the also brief once more mutually homogenize of C.Regulate pH value to 6-7.
Hair repair process agent
The sad 16/octadecane ester of A 0.20 Luvitol EHO
3.00 polymer 1f)
0.10 phytantriol phytantriol
2.00 Cremophor CO 40 PEG-40 castor oil hydrogenated
An amount of aromatic oil of B
2.00 Luviquat Mono LS methylsulfuric acid cocoyl trimethyl ammonium
C 79.70 removes the fossil water demineralized water
D??2.00??Luviquat?FC?905?????????Polyquaternium-16
1.00 silicone oil SF 1288 dimethicone copolyols
An amount of antiseptic
10.00 96% ethanol ethanol
An amount of citric acid citric acid
Preparation:
Mix respectively A mutually with B mutually.With C be stirred to mutually B mutually in.With B and C solution stirring mutually to A mutually in.Adding D also stirs till multiviscosisty mutually.Regulate pH value to 4-5.
Hair jelly
A 0.50 Glucamate SSE-20 polyoxyethylene (20) methyl glucose ether sesquialter stearic acid
Ester
The addition of C remophor CO 40 PEG-40 castor oil hydrogenated
An amount of aromatic oil
30.00 remove the fossil water demineralized water
B??10.00?Luviquat?Hold??????????Polyquaternium-46
2.00??Luviskol?K?90??????????PVP
6.00 polymer 2a)
0.30 Germall 115 imidazolidinyl urea
0.10 Euxyl K 100 benzylalcohols, methyl chloride is for isothiazolone, and methyl is different
Thiazolinone
0.50 D-panthenol USP pantothenylol
5.00??Pluracare?E?6000???????PEG-90
3.00 1,2-propylene glycol Care propylene glycol
40.10 remove the fossil water demineralized water
C 2.50 Natrosol 250 HR hydroxyethyl-celluloses
Preparation:
Dissolving A phase, dissolving B mutually and with its be stirred to A mutually in.C is stirred in A and the B solution mutually mutually.
Silk?hair?cocktail
A 3.00 Luvigel EM caprylic/capric triglycerides, acrylic ester copolymer
Thing
Polymer 2a) 3.00 (anhydrous)
0.50 Wacker Belsil DMC 6031 dimethicone copolyols
2.00 Wacker Belsil DM 1000 polydimethylsiloxane
3.00 Wacker Belsil CM 1000 cyclomethicones, the poly dimethyl silanol
2.00 the amino-terminated polydimethylsiloxane of Wacker Belsil ADM 6057E, spermaceti
The base trimethyl ammonium chloride, the tridecyl polyoxyethylene
(10) ether
2.00 Wacker Belsil PDM 200 Silicone DC 556s
1.00 macadimia nut oil Australia (Ternifolia) macadamia nut oil
0.50 vitamin e acetate vitamin e acetate
1.00 Cremophor CO 40 PEG-40 castor oil hydrogenated
An amount of aromatic oil
B 77.54 demineralized water demineralized waters
0.46 AMP amino methyl propanol
4.00 Luviflex Silk PEG/PPG-25/25 polydimethylsiloxane/third
The olefin(e) acid ester copolymer
An amount of antiseptic
Preparation:
Each component of A phase is mixed dissolving B phase.With B evenly be stirred to mutually A mutually in.
Glossy wetting agent
A 2.00 spermol hexadecanols
1.00 Solan ELD polyoxyethylene (75) lanoline
4.00 glyceryl monostearate tristerin
1.00??Cremophor?A?25????????Ceteareth-25
4.00 the sad 16/octadecane ester of Luvitol EHO
B 10.00 87% glycerol glycerol
5.00 polymer 2b)
2.00 1,2-propylene glycol Care propylene glycol
1.00 Luviquat Mono LS methylsulfuric acid cocoyl trimethyl ammonium
1.50 the poly dimethyl that the polysiloxane microemulsion TMS is amino-terminated
Siloxanes, SM 2115 octyl phenol polyoxy ethylene
(40) ether, different lauryl polyoxyethylene (6) ether, glycerol
1.00 Cremophor PS 20 anhydrous sorbitol polyoxyethylene (20) ether laurates
67.00 remove the fossil water demineralized water
C 0.50 D-panthenol USP pantothenylol
An amount of antiseptic
An amount of aromatic oil
An amount of citric acid citric acid
Preparation:
A is heated to about 80 ℃ respectively mutually with B mutually.With B be stirred to mutually A mutually in and carry out homogenize.Be cooled to about 40 ℃, add C and also carry out homogenize mutually once more.
High glaze typing cream
A 5.00 spermol hexadecanols
10.00 Tegin tristerin SE
5.00 isopropyl myristate isopropyl myristate
An amount of antiseptic
1.00 Dow Corning 200 liquid polydimethylsiloxane
B 5.00 87% glycerol glycerol
5.00 polymer 2b)
0.20 Edeta BD EDTA disodium
2.00??Luviskol?K?30?????????PVP
66.80 remove the fossil water demineralized water
An amount of aromatic oil of C
Preparation:
A is heated to about 80 ℃ respectively mutually with B mutually.With B be stirred to mutually A mutually in and carry out homogenize.Be cooled to about 40 ℃, add C and also carry out brief homogenize mutually once more.
Long-acting setting lotion
A 70.95 removes the fossil water demineralized water
3.00 polymer 2c)
0.20 Tego Betain L 7 cocoyl amido propyl betaines
0.20 Cremophor PS 20 anhydrous sorbitol polyoxyethylene (20) ether laurates
1.25??Luviquat?FC?905???????Polyquaternium-16
0.20 Edeta BD EDTA disodium
0.20 Natrosol 250 HR hydroxyethyl-celluloses
B 8.00 80% thioglycolic acid thioglycolic acids
C 11.00 25% ammonium salt solution ammonium hydroxide
D 5.00 ammonium carbonate ammonium carbonate
Preparation:
Weigh up each component and the stirring of A phase.With B be stirred to mutually A mutually in.
Long-acting setting lotion nertralizer
A 1.00 Cremophor CO 40 PEG-40 castor oil hydrogenated
0.20 aromatic oil
2.0 polymer 2c)
91.60 remove the fossil water demineralized water
B 0.20 Tego Betain L 7 cocamidopropyl betaine
0.20??Cremophor?A?25???????????Ceteareth-25
2.50??Luviquat?FC?905??????????Polyquaternium-16
An amount of antiseptic
C 2.30 hydrogen peroxide 30% hydrogen peroxide
An amount of phosphoric acid 85% phosphoric acid of D
Preparation:
Dissolving A phase, each component that adds the B phase is in succession also mixed.Adding C stirs mutually and once more.Regulate pH value to 3.0-3.5.

Claims (5)

1. the purposes of the polymer of following component in cosmetic formulations:
1-98.9 the caprolactam of weight % (monomer A),
1-98.9 the vinyl pyrrolidone of weight % (monomers B),
0.1-5 the vinyl imidazole of weight % (monomer C),
The monomer D of 0-10 weight %,
The polymer E of 0-10 weight % (based on monomeric total amount),
Wherein the weight ratio of monomer C and monomers B was less than 1: 12.
2. according to the purposes of claim 1, wherein polymer is made of following component:
The monomer A of 30-59 weight %,
The monomers B of 40-69 weight %,
1-4.9 the monomer C of weight %,
The monomer D of 0-10 weight %,
The polymer E of 0-10 weight % (based on monomeric total amount).
3. according to the purposes of claim 1 or 2, be used for the hair cosmetic preparation, in hair setting composition and shampoo.
4. according to the purposes of claim 1 or 2, be used for the cosmetics for skin preparation.
5. hair fixing preparation that especially is foam, mousse, spray or gel form, use therein active component is the polymer according to claim 1 or 2.
CNB038231859A 2002-09-27 2003-09-18 Use of polymers based on N-vinyl caprolactam Expired - Fee Related CN100515383C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10245586.4 2002-09-27
DE10245586A DE10245586A1 (en) 2002-09-27 2002-09-27 Use of polymers based on N-vinylcaprolactam

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CN1684658A true CN1684658A (en) 2005-10-19
CN100515383C CN100515383C (en) 2009-07-22

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EP (1) EP1545445A1 (en)
JP (1) JP2006503075A (en)
CN (1) CN100515383C (en)
AU (1) AU2003273900A1 (en)
DE (1) DE10245586A1 (en)
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CN115353932A (en) * 2022-09-07 2022-11-18 江门市和馨香精技术有限公司 Essence composition for controlling saponification speed, application thereof and cold soap

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US20050281774A1 (en) 2005-12-22
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JP2006503075A (en) 2006-01-26
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DE10245586A1 (en) 2004-04-08
EP1545445A1 (en) 2005-06-29

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